CN106659159A - Herbicidal triazoles - Google Patents

Abstract

The present invention discloses compounds of formula 1, including all stereoisomers thereof, N-oxides and salts thereof, wherein A, X and Y are as defined in this disclosure. The present invention also discloses a composition comprising a compound of formula 1 and a method for controlling undesired vegetation, said method comprising contacting said undesired vegetation or its environment with an effective amount of a compound or composition of the present invention .

Description

Herbicide triazole

technical field

This invention relates to certain triazoles, their N-oxides, salts and compositions, and methods of their use for controlling undesired vegetation.

Background technique

Controlling unwanted vegetation is extremely important to achieve high crop efficiency. Achieving selective control of the growth of weeds is highly desirable, especially in useful crops such as rice, soybean, sugar beet, corn, potato, wheat, barley, tomato and plantation crops, among others. Uncontrolled weed growth in such useful crops can cause a significant reduction in yield, resulting in increased costs to the consumer. It is also important to control undesired vegetation in non-cultivated areas. Many products are commercially available for this purpose, but there is a continuing need for new compounds that are more effective, more economical, less toxic, safer for the environment or have a different site of action.

Contents of the invention

The present invention relates to compounds of formula 1 (including all stereoisomers), their N-oxides and salts thereof, agricultural compositions comprising them, and their use as herbicides:

in

X is R ¹ , and Y is -Q ¹ -J ¹ ; or X is -Q ² -J ² , and Y is R ² ;

R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₄ hydroxyalkyl or C ₃ -C ₆ ring alkyl;

Q ¹ is C(R ⁴ )(R ⁵ ), O, S or NR ⁶ ;

R ² is halogen, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ Haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, C ₂ -C ₆ alkylcarbonyloxy, C ₁ -C ₄ hydroxyalkyl, S(O) _n R ³ , C ₂ -C ₄ alkylthioalkyl, C ₂ -C ₄ alkylsulfonylalkyl, C ₁ -C ₄ alkylamino, C ₂ -C ₄ dialkylamino or C ₃ -C ₆ cycloalkyl;

Q ² is C(R ^4′ )(R ^5′ );

Each of J and J is independently phenyl substituted with ¹ R ⁷ and optionally substituted with up to ² R ⁸ ; or substituted with 1 R ⁷ and optionally substituted with at most 6-membered aromatic heterocyclic ring substituted by 2 R ⁸ ; or substituted by 1 R ⁹ on a carbon ring member and R ¹¹ on a nitrogen ring member and optionally substituted by 1 R ¹⁰ on a carbon ring member The 5-membered aromatic heterocyclic ring;

A is phenyl substituted by up to 4 R ¹⁶ ; or a 5- or 6-membered aromatic heterocyclic ring substituted by up to 3 R ¹⁶ on the carbon ring member and R ¹⁷ on the nitrogen ring member;

R ³ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Each R ⁴ and R ^4' is independently H, F, Cl, Br, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or CO ₂ R ¹³ ;

Each R ⁵ and R ^5' is independently H, F, C ₁ -C ₄ alkyl, OH or OR ¹³ ; or R ⁴ and R ⁵ or R ^4' and R ^5' are bonded to the carbon to which they are attached together to form C(=O), C(=NOR ¹³ ) or C(=NN(R ¹⁴ )(R ¹⁵ ));

R ⁶ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or S(O) _p R ¹⁸ ;

Each R ⁸ is independently halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, or S(O) _p R ¹⁹ ; or R ⁷ and R ⁸ taken together to form a 5-membered carbocyclic ring comprising ring members selected from up to two O atoms or up to two S atoms, and optionally between carbon atoms Ring members are substituted by up to five halogen atoms;

R ⁹ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, or S(O) _p R ¹⁸ at the meta position where the ring is attached to the rest of Formula 1;

R ¹⁰ is halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or S(O) _p R ¹⁹ ;

R ¹¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

each R ¹³ is independently C ₁ -C ₄ alkyl;

R ¹⁴ is C1-C4 alkyl or C1-C4 haloalkyl;

R ¹⁵ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Each R ¹⁶ is independently H, halogen, cyano, nitro, SF ₅ , C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy or S(O) _p R ²⁰ ;

Each R ¹⁷ is independently H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Each R ¹⁸ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Each R ¹⁹ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

R ²⁰ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

n is 0 or 1; and each p is independently 0, 1 or 2;

The proviso is that when R1 is ethyl and Q1 is _CH2 , then J1 is not ³ -trifluoromethyl- ^1H -pyrazol- ¹ -yl.

More specifically, the present invention relates to compounds of formula 1 (including all stereoisomers), N-oxides or salts thereof. The present invention also relates to herbicidal compositions comprising a compound of the present invention (ie in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. The present invention also relates to methods for controlling undesired vegetation growth comprising contacting said vegetation or its environment with a herbicidally effective amount of a compound of the present invention, for example in the form of a composition described herein.

The present invention also includes a herbicidal mixture comprising (a) a compound selected from formula 1, N-oxides and salts thereof, and (b) at least one additional active ingredient, said additional active Components selected from (b1) to (b16) and salts of compounds of (b1) to (b16).

detailed description

As used herein, the terms "comprises," "comprising," "comprising," "having," "contains," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any expressly stated limitations as a condition. For example, a composition, mixture, process, method, article, or apparatus comprising a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed, or such compositions, mixtures, processes, methods, Element inherent in an article or device.

The connective phrase "consisting of" does not include any unspecified element, step or ingredient. If in a claim, such words limit the claim to exclude materials other than those stated except for impurities which usually accompany them. When the phrase "consisting of" appears in a clause of the body of a claim, rather than immediately before the preamble, it restricts only the elements mentioned in that clause; other elements are not excluded from the claim as a whole. exclude.

The linking phrase "consisting essentially of" is used to define that the composition, method or apparatus includes substances, steps, parts, components or elements in addition to those literally disclosed, provided that such additional substances, steps , parts, components or elements will not substantially affect the basic and novel features of the claimed invention. The term "consisting essentially of" is intermediate between "comprising" and "consisting of".

When applicants use open-ended terms such as "comprising" to define an invention or portions thereof, it should be readily understood that (unless otherwise indicated) this description should be construed as also using the terms "consisting essentially of" or "consisting essentially of" or "Consisting of" describes the invention.

Furthermore, unless expressly stated to the contrary, "or" means an inclusive "or" rather than an exclusive "or". For example, condition A or B satisfies any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

Additionally, the indefinite article "a", "an" preceding an element or component of the invention is not intended to limit the number of instances (ie, occurrences) of that element or component. Therefore, "a", "an" should be understood to include one or at least one, and the singular word form of an element or component also includes the plural, unless the numerical value is clearly meant to be singular.

As referred to herein, the term "seedling" used alone or in combination of words refers to a plant seedling that develops from the embryo of a seed.

As referred to herein, the term "broadleaf" may be used alone or in terms such as "broadleaf weed" to refer to dicotyledonous or dicotyledonous plants, a term used to describe a class of angiosperm plants whose Characterized by an embryo with two cotyledons.

As used herein, the term "alkylating agent" refers to a chemical compound in which a carbon-containing group is bonded through a carbon atom to a leaving group, such as a halogen or a sulfonate, which can be bonded to by a nucleophile. The carbon atoms are bonded and replaced. Unless otherwise indicated, the term "alkylation" does not limit the carbon-containing group to an alkyl group; the carbon ^- containing group in the alkylating agent includes the various carbon ^- linked substituents specified for R and Q.

In the above expressions, the term "alkyl" used alone or in compound words such as "alkylthioalkyl" and "haloalkyl" includes straight-chain or branched-chain alkyl groups such as methyl, ethyl, n-propyl , isopropyl or different butyl isomers. "Alkenyl" includes straight or branched chain alkenes such as vinyl, 1-propenyl, 2-propenyl and the different butenyl isomers. "Alkenyl" also includes polyalkenes such as 1,2-propadienyl. "Alkynyl" includes straight or branched chain alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl isomers.

"Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy isomers. "Alkoxyalkyl" means an alkoxy substituent on an alkyl group. Examples _of " _alkoxyalkyl " _{include CH3OCH2} , _CH3OCH2CH2 , _{CH3CH2OCH2 ,} and _{CH3CH2OCH2CH2} . "Alkenyloxy" includes straight or branched chain alkenyloxy moieties. Examples of "alkenyloxy" include _H2C =CHCH2O, ( _{CH3 ) CH} = _CHCH2O , and _CH2 = _CHCH2CH2O . "Alkynyloxy" includes straight or branched chain alkynyloxy moieties. Examples of "alkynyloxy" include _HC≡CCH2O and _CH3C≡CCH2O . Examples of "alkanesulfonyl" include CH ₃ S(O) ₂ -, CH ₃ CH ₂ S(O) ₂ -, CH ₃ CH ₂ CH ₂ S(O) ₂ -, (CH ₃ ) ₂ CHS(O) ₂ -, and different butylsulfonyl isomers. "Alkylthioalkyl" means alkylthio substitution on an alkyl group. Examples of "alkylthioalkyl" include CH ₃ SCH ₂ , CH ₃ SCH ₂ CH ₂ , CH ₃ CH ₂ SCH ₂ and CH ₃ CH ₂ SCH ₂ CH ₂ . "Alkylamino" and "dialkylamino" are defined similarly to the examples above.

"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen" alone or in compound words such as "haloalkyl" or when used in descriptions such as "alkyl substituted by halogen" includes fluorine, chlorine, bromine or iodine. Also, when used in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted by halogen", the alkyl group may be represented by a halogen atom (which may be the same or different) Partially or completely replaced. Examples of "haloalkyl" or "alkyl substituted by halogen" include F ₃ C, ClCH ₂ , CF ₃ CH ₂ and CF ₃ CCl ₂ . The term "haloalkoxy" is defined similarly to the term "haloalkyl". Examples of "haloalkoxy" include CF ₃ O-, CCl ₃ CH ₂ O-, HCF ₂ CH ₂ CH ₂ O-, and CF ₃ CH ₂ O-.

"Alkylcarbonyl" means a straight or branched chain alkyl moiety bonded to a C(=O) moiety. Examples of "alkylcarbonyl" include CH ₃ C(=O)-, CH ₃ CH ₂ CH ₂ C(=O)-, and (CH ₃ ) ₂ CHC(=O)-. Examples of "alkoxycarbonyl" include CH ₃ OC(=O)-, CH ₃ CH ₂ OC(=O)-, CH ₃ CH ₂ CH ₂ OC(=O)-, (CH ₃ ) ₂ CHOC(= O)- and the different butoxy- or pentyloxycarbonyl isomers.

The total number of carbon atoms in a substituent group is indicated by the "C _i -C _j " prefix, where i and j are numbers from 1 to 6. For example, C ₁ -C ₄ haloalkoxy is designated as halomethoxy to halobutoxy; C ₂ alkoxyalkyl is designated as CH ₃ OCH ₂ —; C ₃ alkoxyalkyl is designated as, for example, CH ₃ CH(OCH ₃ )-, CH ₃ OCH ₂ CH ₂ - or CH ₃ CH ₂ OCH ₂ -; and C ₄ alkoxyalkyl designates an alkane substituted with an alkoxy group containing a total of four carbon atoms Various isomers of radical groups, examples include CH ₃ CH ₂ CH ₂ OCH ₂ — and CH ₃ CH ₂ OCH ₂ CH ₂ —.

When a fully unsaturated carbocyclic ring satisfies Huckel's law, then the ring is also referred to as an "aromatic ring".

The term "heterocyclic ring", "heterocycle" or "heterocyclic ring system" means a ring or ring system in which at least one atom forming the backbone of the ring is other than carbon (eg, nitrogen, oxygen or sulfur). Typically, heterocyclic rings contain no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise specified, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Huckel's law, then the ring is also referred to as a "heteroaromatic ring" or "aromatic heterocyclic ring".

"Aromatic" means that the ring atoms are substantially in the same plane and have p-orbitals perpendicular to the plane of the ring, and (4n+2) π electrons (where n is a positive integer) are connected to the ring associated to comply with Hückel's law.

The term "optionally substituted" in relation to a heterocyclic ring refers to a group which is unsubstituted or has at least one non-hydrogen substituent which does not destroy the biological activity possessed by the unsubstituted analog. As used herein, unless otherwise indicated, the following definitions apply. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted". Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.

As mentioned above, A may be, among others, phenyl optionally substituted with one or more substituents selected from the substituents as defined in the Summary of the Invention. An example of phenyl optionally substituted by one to four substituents is the ring shown in U-1 in Example 1, wherein ^Rv is ^R16 as defined for A in the Summary of the Invention, and r is an integer (0 to 4 ).

As stated above, A may be (among others) a 5- or 6-membered aromatic heterocyclic ring optionally substituted with one or more substituents selected from the substituents as defined in the Summary of the Invention . Examples of 5-membered or 6-membered unsaturated aromatic heterocyclic rings optionally substituted by one or more substituents include rings U-2 to U-61 shown in Example 1, wherein ^Rv is Any substituent as defined by A (ie R ¹⁶ or R ¹⁷ ), and r is an integer from 0 to 4, limited by the number of available positions on each U group. Since there is only one available position for U-29, U-30, U-36, U-37, U-38, U-39, U40, U-41, U-42 and U-43, for these U group, r is limited to the integer 0 or 1, and r being 0 means that the U group is unsubstituted and there is a hydrogen at the position indicated by (R ^v ) _r .

Example 1

Although the ^Rv groups are shown in structures U-1 to U-61, it should be noted that they do not have to be present as they are optional substituents. Note that when ^Rv is H, when attached to an atom, it is as if said atom were unsubstituted. Nitrogen atoms requiring substitution to fill their valences are replaced with H or ^Rv . Note that when the point of attachment between ( ^Rv ) _r and the U group is shown floating, ( ^Rv ) _r may be attached to any available carbon or nitrogen atom of the U group. Note that when the point of attachment on a U group is shown floating, the U group can be connected to the remainder of Formula 1 via any available carbon or nitrogen in the U group by replacing a hydrogen atom. Note that some U groups can only be substituted by less than 4 ^Rv groups (eg U-2 to U-5, U-7 to U-48, and U-52 to U-61).

A variety of synthetic methods are known in the art to enable the preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for an extensive review see the eight-volume collection Comprehensive Heterocyclic Chemistry, edited by A.R. Katritzky and C.W. Rees, Pergamon Press, Oxford, pp. 1984 and Comprehensive Heterocyclic Chemistry II in twelve volumes, edited by A.R. Katritzky, C.W. Rees and E.F.V. Scriven, Pergamon Press, Oxford, 1996.

The compounds of the invention may exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers that are identical in composition but differ in the arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also called geometric isomers) and atropisomers Construct. Atropisomers arise from restricted rotation about a single bond, where the rotational barrier is high enough to allow separation of isomeric species. Those skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit Beneficial effect. In addition, those skilled in the art know how to separate, enrich and/or selectively prepare said stereoisomers. The compounds of the present invention may exist as a mixture of stereoisomers, as individual stereoisomers or as optically active forms.

Compounds of Formula 1 generally exist in more than one form, and Formula 1 therefore includes all crystalline and amorphous forms of the compounds they represent. Amorphous forms include solid embodiments such as waxes and gums, and liquid embodiments such as solutions and melts. Crystalline forms include embodiments that represent substantially a single crystal form, and embodiments that represent a mixture of polymorphs (ie, different crystal forms). The term "polymorph" refers to a specific crystal form of a compound that can crystallize in different crystal forms having different molecular arrangements and/or molecular conformations in the crystal lattice. Although polymorphs can have the same chemical composition, they can also have different compositions due to the presence or absence of co-crystallized water or other molecules that can bind weakly or strongly in the crystal lattice. Polymorphs can have different chemical, physical, and biological properties, such as crystalline shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. Those skilled in the art will appreciate that a polymorphic form of a compound of Formula 1 may exhibit beneficial effects relative to another polymorphic form or mixture of polymorphic forms of the same compound of Formula 1 (e.g., for the preparation of Formulation suitability, improved biological properties). The preparation and isolation of particular polymorphs of the compound of formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using the chosen solvent and temperature. For an extensive discussion of polymorphisms see Polymorphism in the Pharmaceutical Industry, edited by R. Hilfiker, Wiley-VCH, Weinheim, 2006.

Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires an available lone pair of electrons to be oxidized to oxides; those skilled in the art will recognize that N-oxides can form - Those nitrogen-containing heterocyclic rings of oxides. Those skilled in the art will also know that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are well known to those skilled in the art and include the use of peroxyacids such as peracetic acid and m-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, Alkyl hydroperoxides (such as t-butyl hydroperoxide), sodium perborate, and dioxiranes (such as dimethyldioxirane) oxidize heterocyclic compounds and tertiary amines. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T.L. Gilchrist in Comprehensive Organic Synthesis, Vol. 7, pp. 748–750, edited by S.V. Ley, Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry Vol. 3, pp. 18–20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimmett and B.R.T. Keene in Advances in Heterocyclic Chemistry, Vol. 43, pp. 149–161, edited by A.R. Katritzky , Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry vol. 9, pp. 285–291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and G.W.H. Cheeseman and E.S.G. Pages 390–392, edited by A.R. Katritzky and A.J. Boulton, Academic Press.

Those skilled in the art recognize that salts and non-salt forms of compounds share biological utility because salts and their corresponding non-salt forms are in equilibrium under environmental and physiological conditions. Thus, various salts of the compounds of formula 1 can be used to control undesired vegetation (ie are agriculturally suitable). Salts of compounds of formula 1 include acid-addition salts formed with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, malic, acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid. When the compound of Formula 1 contains an acidic moiety such as carboxylic acid or phenol, salts also include combinations with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, or sodium, potassium, lithium, calcium, magnesium or barium. Those formed from hydrides, hydroxides or carbonates. Accordingly, the present invention includes compounds selected from Formula 1, N-oxides thereof, and agriculturally suitable salts thereof.

Embodiments of the invention as described in the Summary of the Invention include (wherein Formula 1 as used in the following embodiments includes N-oxides and salts thereof):

Embodiment 1: Compounds of formula 1 (including all stereoisomers), N-oxides and salts thereof, agricultural compositions comprising them and their use as herbicides, as described in the summary of the invention.

Embodiment 1a. A compound of Embodiment 1 wherein X is R ¹ and Y is -Q ¹ -J ¹ .

Embodiment 1b. A compound of Embodiment 1 wherein X is -Q ² -J ² and Y is R ² .

Embodiment 2: A compound of Embodiment 1, wherein R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkynyl.

Embodiment 3: A compound of Embodiment 2, wherein R ¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.

Embodiment 4. A compound of Embodiment 3, wherein R ¹ is C ₁ -C ₄ alkyl.

Embodiment 5. A compound of Embodiment 4, wherein R ¹ is propyl, ethyl or methyl.

Embodiment 6. A compound of Embodiment 5 wherein R ¹ is propyl.

Embodiment 7. A compound of any one of Embodiments ¹ to ⁶ , wherein Q1 is C(R4)(R5 ⁾ or O.

Embodiment 8. A compound of Embodiment ⁷ , wherein Q1 is C(R4 ⁾ (R5 ⁾ .

Embodiment 9. A compound of Embodiment 7 wherein Q ¹ is O.

Embodiment 10. The compound of any one of Embodiments ¹ to ⁶ , wherein Q1 is NR6.

Embodiment 11. A compound of any one of Embodiments 1 to 8, wherein R ⁴ is H, F or C ₁ -C ₄ alkyl.

Embodiment 11a. A compound of Embodiment ¹¹ wherein R4 is H.

Embodiment 12. A compound of any one of Embodiments 1 to 8, wherein R ⁵ is H, F, C ₁ -C ₄ alkyl or OH.

Embodiment 12a. A compound of Embodiment ¹² wherein R5 is H or OH.

Embodiment 13. A compound of Embodiment 12, wherein R ⁵ is H.

Embodiment 14. A compound of any one of Embodiments 1 to 8, wherein when R ⁴ and R ⁵ are taken together with the carbon to which they are attached to form C(=O), C(=NOR ¹³ ) or C(= NN(R ¹⁴ )(R ¹⁵ ));

Embodiment 15. A compound of Embodiment 1 wherein R ⁶ is H or C ₁ -C ₄ alkyl.

Embodiment 16. A compound of Embodiment ₁₅ wherein R6 is ^CH3 .

Embodiment 17. A compound of Embodiment 15, wherein R ⁶ is H.

Embodiment 18: A compound of Embodiment 1, wherein R ² is C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkyl , C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, C ₂ -C ₄ alkylthio ylalkyl or C ₃ -C ₆ cycloalkyl.

Embodiment 19: A compound of Embodiment 18, wherein R ² is C _1- C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.

Embodiment 20. A compound of Embodiment 19, wherein R ² is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl.

Embodiment 21. A compound of Embodiment 20, wherein R ² is C ₁ -C ₄ alkoxy.

Embodiment 22. A compound of Embodiment 20, wherein R ² is C ₁ -C ₄ alkyl.

Embodiment 23. A compound of Embodiment 21 wherein R ² is ethoxy or methoxy.

Embodiment 24. A compound of Embodiment 23 wherein R ² is ethoxy.

Embodiment 25. A compound of Embodiment 22, wherein R ² is ethyl or propyl.

Embodiment 26. A compound of Embodiment 25 wherein R ² is propyl.

Embodiment 27. A compound of Embodiment 1 or any one of Embodiments 18 to 26 wherein ^Q2 is C(R4 ^' )(R5 ^' ).

Embodiment 27a. A compound of Embodiment 27 wherein R ^4' is independently H, F, Cl, Br, C ₁ -C ₄ alkyl or CO ₂ R ¹³ .

Embodiment 27b. A compound of Embodiment 27a wherein R ^4' is independently H, F, Cl, C ₁ -C ₄ alkyl.

Embodiment 27c. A compound of Embodiment 27b wherein R ^4' is independently H, F, Cl, CH ₃ or CH ₂ CH ₃ .

Embodiment 27d. A compound of Embodiment 27c wherein R ^4' is independently H, F, CH ₃ or CH ₂ CH ₃ .

Embodiment 27e. A compound of Embodiment 27d wherein R4 ^' is independently H, F or _CH3 .

Embodiment 28. A compound of Embodiment 27 wherein R ^4' is H.

Embodiment 28a. A compound of Embodiment ²⁷ wherein R5 ^' is H, F, _CH3 , _CH2CH3 , OH or _OR13 .

Embodiment 28b. A compound of Embodiment ^28a wherein R5 ^' is H, F, _CH3 or _CH2CH3 or _OR13 .

Embodiment 28c. _A compound of Embodiment 28b wherein R5 ^' is H, F, _CH3 or _CH2CH3 .

Embodiment 28d. A compound of Embodiment 28c wherein R5 ^' is H, F or _CH3 .

Embodiment 29. A compound of Embodiment 27 wherein R ^5' is H or OH.

Embodiment 30. A compound of Embodiment 29 wherein R ^5' is H.

Embodiment 31. A compound of Embodiment 27 wherein R ^4' and R ^5' are taken together with the carbon to which they are attached to form C(=O), C(=NOR ¹³ ) or C(=NN(R ¹⁴ ) (R ¹⁵ )).

Embodiment 32. ^A compound of any one of Embodiments ¹ to 31, wherein each J or J is independently selected from

Embodiment 33. A compound of Embodiment 32 wherein each J1 or J2 is selected from J ^{- 1} to J-14 (ie, phenyl or 6-membered heteroaromatic ring).

Embodiment 34. A compound of Embodiment 32, wherein J ¹ or J ² is selected from J-15 to J-33 (ie a 5 membered heteroaromatic ring).

Embodiment 35. A compound of Embodiment 33, wherein J1 or J2 is selected from J- ¹ and J- ² .

Embodiment 36. A compound of Embodiment 35 wherein J1 or J2 is J ^{- 1} .

Embodiment 37. A compound of Embodiment 35 wherein J1 or J2 is J ^{- 2} .

Embodiment 38. A compound of Embodiment 36 wherein J1 is J- ¹ .

Embodiment 39. A compound of Embodiment 38 wherein J1 is J- ¹ and ^R7 is _CF3 .

Embodiment 40. A compound of Embodiment 37 wherein J1 is J- ² .

Embodiment 41. A compound of Embodiment 40 wherein J1 is J- ² and ^R7 is _CF3 .

Embodiment 42. A compound of Embodiment 36 wherein J2 is J- ¹ .

Embodiment 43. A compound of Embodiment 42 wherein J2 is J- ¹ and ^R7 is _CF3 .

Embodiment 44. A compound of Embodiment 37 wherein J2 is J- ² .

Embodiment 45. A compound of Embodiment 44 wherein J2 is J- ² and ^R7 is _CF3 .

Embodiment 45A. A compound of Formula ¹ wherein each J and J is independently a ⁶ membered aromatic heterocyclic ring substituted with 1 R ⁷ and optionally substituted with up to 2 R ⁸ on carbocyclic ring members or a 5 membered aromatic heterocyclic ring substituted by 1 R ⁹ on a carbon ring member and R ¹¹ on a nitrogen ring member and optionally substituted by 1 R ¹⁰ on a carbon ring member.

Embodiment 45B. A compound of Embodiment 45A wherein J is a 6 membered aromatic heterocyclic ring substituted by ¹ R ⁷ and optionally substituted by up to 2 R ⁸ on a carbocyclic ring member; or by a carbocyclic member A 5-membered aromatic heterocyclic ring substituted with 1 R ⁹ on and R ¹¹ on a nitrogen ring member and optionally substituted with 1 R ¹⁰ on a carbon ring member.

Embodiment 45C. A compound of Embodiment 45B wherein J ¹ is a 6 membered aromatic heterocyclic ring substituted with 1 R ⁷ and optionally substituted with up to 2 R ⁸ on carbocyclic ring members.

Embodiment 45D. A compound of Embodiment 45A wherein J is a ⁶ membered aromatic heterocyclic ring substituted by 1 R and optionally substituted by up to ² R ^on a carbocyclic member; or by a carbocyclic member A 5-membered aromatic heterocyclic ring substituted with 1 R ⁹ on and R ¹¹ on a nitrogen ring member and optionally substituted with 1 R ¹⁰ on a carbon ring member.

Embodiment 45E. A compound of Embodiment 45D wherein J ² is a 6 membered aromatic heterocyclic ring substituted with 1 R ⁷ and optionally substituted with up to 2 R ⁸ on carbocyclic ring members.

Embodiment 45F. A compound of Embodiment 45D wherein J is ⁵ substituted by 1 R ^on a carbon ring member and R ¹¹ on a nitrogen ring member and optionally substituted by 1 R ¹⁰ on a carbon ring member membered aromatic heterocyclic ring.

Embodiment 45G. ^A compound of any one of Embodiments ¹ to 31, wherein each J or J is independently selected from

Embodiment 45H. A compound of Embodiment 45G wherein each J ¹ or J ² is selected from J-2 to J-14 (ie a 6 membered heteroaromatic ring).

Embodiment 45I. A compound of Embodiment 45G wherein J1 or J2 is selected from J ^{- 15} to J-33 (ie a 5 membered heteroaromatic ring).

Embodiment 45J. A compound of Embodiment 45G, wherein J or J is selected from J ^{- 2} , J-3, J-4, J-5, J-6, J-7, J-9, J-12, J-17, J-18, J-20, J-22, J-26, J-29 and J-30.

Embodiment 45K. A compound of Embodiment 45J wherein J1 or J2 is selected from J ^{- 2} , J-12, J-17, J-18, J-20 and J-22.

Embodiment 45L. A compound of Embodiment 45J wherein J1 or J2 is selected from J ^{- 2} , J-20 and J-22.

Embodiment 45M. A compound of Embodiment 45J wherein J1 or J2 is J ^{- 2} .

Embodiment 45N. A compound of Embodiment 45J wherein J1 or J2 is J ^{- 22} .

Embodiment 45O. A compound of Embodiment 45J wherein J1 is J- ² and ^R7 is _CF3 .

Embodiment 45P. A compound of Embodiment 45J wherein J2 is J- ² .

Embodiment 45Q. A compound of Embodiment 45J wherein J2 is J- ² or _CF3 .

Embodiment 45R. A compound of Formula 1 or any one of Embodiments 1 to ^45Q wherein A is a 5- or 6-membered aromatic substituted by up to 3 R on ^a carbon ring member and R on a nitrogen ring member heterocyclic ring.

Embodiment 45S: The compound of 45R wherein A is a 6 membered aromatic heterocyclic ring substituted with up to 3 R ¹⁶ on carbon ring members and R ¹⁷ on nitrogen ring members.

Embodiment 45T. A compound of Embodiment 45R wherein A is a 5 membered aromatic heterocyclic ring substituted with R ¹⁶ on up to 3 carbon ring members and R ¹⁷ on nitrogen ring members.

Embodiment 45U. A compound of Embodiment 45T wherein A is not a substituted 1H-pyrazol-5-yl moiety.

Embodiment 46. A compound of any one of Embodiments 1 to 45 wherein A is phenyl substituted with up to 3 R ¹⁶ .

Embodiment 47. A compound of Embodiment 46 wherein A is phenyl substituted with up to 2 R ¹⁶ .

Embodiment 48. A compound of Embodiment 47 wherein A is phenyl substituted with 1 R ¹⁶ .

Embodiment 49. A compound of Embodiment 48 wherein R ¹⁶ is at the para position where the benzene ring is attached to the rest of Formula 1.

Embodiment 50. A compound of any one of Embodiments 38, 40, 42 and 44, wherein R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkane Oxygen.

Embodiment 51. A compound of Embodiment 50, wherein R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy.

Embodiment 52. A compound of Embodiment 51 wherein R ⁷ is C ₁ -C ₄ haloalkyl.

Embodiment 53. A compound of Embodiment 52 wherein ^R7 is _CF3 .

Embodiment 54. A compound of Embodiment 51 wherein R ⁷ is C ₁ -C ₄ alkoxy.

Embodiment 55. A compound of Embodiment 51 wherein R ⁷ is C ₁ -C ₄ haloalkoxy.

Embodiment 56. A compound of any one of Embodiments 1 to 55 wherein each R ⁸ is independently halogen or C ₁ -C ₄ haloalkyl.

Embodiment 57. A compound of Embodiment 56 wherein each ^R8 is independently F, Cl or _CF3 .

Embodiment 58. A compound of Embodiment 57 wherein each R ⁸ is F.

Embodiment 59. The compound of any one of Embodiments 1 to 58 wherein each R ¹³ is independently CH ₃ .

Embodiment 60. A compound of Embodiment 47, wherein each R ¹⁶ is independently halogen, cyano, SF ₅ , C _1- C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkane group, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkynyl.

Embodiment 60a. A compound of Embodiment 60 wherein each R ¹⁶ is independently halogen or C ₁ -C ₄ haloalkyl.

Embodiment 60b. A compound of Embodiment 60a wherein each R ¹⁶ is independently halogen.

Embodiment 61. A compound of Embodiment 48, wherein R ¹⁶ is halogen, cyano, SF ₅ , C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkynyl.

Embodiment 61a. A compound of Embodiment 61 wherein R ¹⁶ is C ₁ -C ₄ haloalkyl or halogen.

Embodiment 62. A compound of Embodiment 61a wherein R ¹⁶ is CF ₃ or F.

Embodiment 63. A compound of Embodiment 62 wherein R ¹⁶ is at the para position where the benzene ring is attached to the remainder of Formula 1.

Embodiment 64: A compound of Formula 1 other than 4-[[3-[3,5-bis(trifluoromethyl)phenyl]-1-methyl-1H-1,2,4-triazole-5- thio]-6-chloro-2-(methylthio)-pyrimidine (CAS#1508257-65-5).

Embodiment 65. A compound of Formula 1, provided that when A is phenyl substituted with 1 R ¹⁶ , X is R ¹ , and Y is -Q ¹ -J ¹ , R ¹ is ethyl, and Q ¹ is When CH ₂ , then J ¹ is not 3-trifluoromethyl-1H-pyrazol-1 base.

Embodiments of the invention, including embodiments 1-65 above as well as any other embodiments described herein, may be combined in any manner, and the variable descriptions in the embodiments refer not only to compounds of formula 1, but also to compounds that can be used in the preparation of formula The starting compound and intermediate compound of the compound of 1. Furthermore, embodiments of the invention, including Embodiments 1-65 above and any other embodiments described herein, and any combination thereof, are suitable for use in the compositions and methods of the invention.

Combinations of Embodiments 1-65 are illustrated by:

Embodiment AB: Compounds of the inventive content of the present invention, wherein J ¹ or J ² are independently selected from

Embodiment AB1: Compounds according to the inventive content of the present invention, wherein J ¹ or J ² are independently selected from

Embodiment 1A. A compound of Embodiment AB, wherein

X is R ¹ , and Y is -Q ¹ -J ¹ ;

R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkynyl;

Q ¹ is C(R ⁴ )(R ⁵ ) or O;

R4 is H ^;

R ⁵ is H or OH;

J1 is selected from J- ¹ and J-2;

R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted with up to 2 R ¹⁶ ; and

Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen.

Embodiment 1A1. A compound of Embodiment AB, AB1 or 1A wherein

X is R ¹ , and Y is -Q ¹ -J ¹ ;

R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkynyl;

Q ¹ is C(R ⁴ )(R ⁵ ) or O;

R4 is H ^;

R ⁵ is H or OH;

R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted with up to 2 R ¹⁶ ; and

Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen.

Embodiment 1B. A compound of Embodiment 1A, wherein

R ¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Q ¹ is C(R ⁴ )(R ⁵ );

R ⁵ is H;

J ¹ is J-1;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted by 1 R ¹⁶ ; and R ¹⁶ is CF ₃ or F.

Embodiment 1C. A compound of Embodiment 1A wherein

R ¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Q ¹ is C(R ⁴ )(R ⁵ );

R ⁵ is H;

J1 is J- ² ;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted by 1 R ¹⁶ ; and R ¹⁶ is CF ₃ or F.

Embodiment 1D. A compound of Embodiment 1A wherein

R ¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

Q ¹ is O;

J1 is selected from J- ¹ and J-2;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted with up to 2 R ¹⁶ ; and

Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen.

Embodiment 1E. A compound of Embodiment 1D wherein

R ¹ is phenyl, ethyl or methyl;

J ¹ is J-1;

^R7 is _CF3 ;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 1F. A compound of Embodiment 1D wherein

R ¹ is phenyl, ethyl or methyl;

J1 is J- ² ;

^R7 is _CF3 ;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 1G: A compound of any one of Embodiments 1B, 1C, 1E and 1F, wherein

R ¹⁶ is at the para position where the benzene ring is attached to the rest of Formula 1.

Embodiment 2A. A compound of Embodiment AB, wherein

X is -Q ² -J ² , and Y is R ² ;

R ² is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl;

Q ² is C(R ^4′ )(R ^5′ );

R ^4' is H;

R ^5' is H;

J ² is selected from J-1 and J-2;

R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted with up to 2 R ¹⁶ ; and

Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen.

Embodiment 2A1. A compound of Embodiment AB, AB1 or 2A wherein

X is -Q ² -J ² , and Y is R ² ;

R ² is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl;

Q ² is C(R ^4′ )(R ^5′ );

R ^4' is H;

R ^5' is H;

R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

A is phenyl substituted with up to 2 R ¹⁶ ; and

Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen.

Embodiment 2B. A compound of Embodiment 2A, wherein

R ² is C ₁ -C ₄ alkoxy;

J ² is J-1;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 2B1. A compound of Embodiment 2A wherein

R ² is C ₁ -C ₄ alkoxy;

J2 is selected from J- ² , J-12, J-17, J-18, J-20 and J-22;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 2C. A compound of Embodiment 2A or 2B1 wherein

R ² is C ₁ -C ₄ alkoxy;

J ² is J-2;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 2D. A compound of Embodiment 2A wherein

R ² is C ₁ -C ₄ alkyl;

J ² is J-1;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 2E. A compound of Embodiment 2A, wherein

R ² is C ₁ -C ₄ alkyl;

J ² is J-2;

R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

^A is phenyl substituted by 1 R; and

R ¹⁶ is CF ₃ or F.

Embodiment 2F. A compound of any one of Embodiments 2B, 2C, 2D and 2E, wherein

R ¹⁶ is at the para position where the benzene ring is attached to the rest of Formula 1.

Particular embodiments include compounds of formula 1 selected from the group consisting of:

4-[[5-Ethyl-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl ) pyridine (compound 1);

4-[[3-(4-fluorophenyl)-5-propyl-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine (compound 6 );

4-[[5-ethoxy-3-(4-fluorophenyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine (compound 8);

4-[[3-(4-fluorophenyl)-1-propyl-1H-1,2,4-triazol-5-yl]methyl]-2-(trifluoromethyl)pyridine (compound 17 ); and 4-[[3-(4-fluorophenyl)-5-methoxy-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl) Pyridine (Compound 9).

The invention also relates to methods for controlling undesired vegetation comprising applying to a locus of vegetation a herbicidally effective amount of a compound of the invention (eg in the form of a composition described herein). Notable embodiments related to methods of use are those involving compounds of the above embodiments. The compounds of the invention are especially useful for the selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, rapeseed and rice, and specialty crops such as sugar cane, citrus, fruit and nut crops.

Also notable embodiments are herbicidal compositions of the invention comprising compounds of the above embodiments.

The present invention also includes herbicidal mixtures comprising (a) compounds selected from formula 1, N-oxides and salts thereof, and (b) at least one additional active ingredient selected from: (b1 ) photosystem II inhibitors, (b2) acetohydroxyacid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimetics, (b5) 5-enes Alcohol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitor, (b6) photosystem I electron diverter, (b7) protoporphyrinogen oxidase (PPO) inhibitor, (b8) glutamine Synthase (GS) Inhibitor, (b9) Very Long Chain Fatty Acid (VLCFA) Elongase Inhibitor, (b10) Auxin Transport Inhibitor, (b11) Phytoene Desaturase (PDS) Inhibitor, ( b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solanidase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides Agents, including mitosis disruptors, organic arsenic-containing compounds, orazam, bromobutyramid, cycloheptafen, benuuron, dacetam, wild swallow, sapuron, etoxybenzamide, imazamin, Phylphosin, fenfofos, metamul, methauron, oleic acid, oxazicone, nonanoic acid and barnclofen, and (b16) herbicide safeners; and (b1) to (b16) Compound salts.

"Photosystem II inhibitors" (bl) are chemical compounds that bind to the _D - ₁ protein at the QB binding site, thereby blocking electron transport from QA to QB in the chloroplast _thylakoid membrane. Electrons blocked by photosystem II are transferred through a series of reactions to form toxic compounds that damage cell membranes and cause chloroplast swelling, membrane leakage, and eventually cell rupture. The Q _B binding site has three distinct binding sites: binding site A binds triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, and binding site B binds phenylureas such as Diuron, and binding site C binds benzothiadiazoles such as bentazone, nitriles such as bromoxynil, and phenyl-pyridazines such as dazat. Examples of photosystem II inhibitors include ametrazine, amiflumezone, atrazine, bentazone, carbazim, bromophenoxime, bromoxynil, chlorobromone, dimethalin, chlorotoluron, subtilon , benuuron, cyanazine, diuron, beetan, diuron, oxazuron, isoamyl ethyl, diuron, sulfhiuron, feuron, fluorumon, hexazinone, iodobenzene Nitrile, isoproturon, isoxauron, cyclopyridine, ligulong, methoxazone, methylbenzthiuron, xiugulong, methoxuron, sikejin, lvgulong, grassbulong, formazan Chloramide, beetenin, prometone, promethazine, propanil, permethazine, pyridafol, pyridafol, cyclomeuron, simazine, xicaojing, buthiuron, teclodine, terdington, tetramide Dingjing, Qucaojing and Caodajin.

"AHAS inhibitors" (b2) are chemical compounds that inhibit acetohydroxyacid synthase (AHAS), also known as acetolactate synthase (ALS), thereby inhibiting branched-chain aliphatic amino acids required for protein synthesis and cell growth Preparations such as valine, leucine and isoleucine to kill plants. Examples of AHAS inhibitors include rimsulfuron-methyl, rimsulfuron-methyl, bensulfuron-methyl, bispyribac, chlorsulfuron-methyl, chlorsulfuron-ethyl, chlorsulfuron-methyl , etesulfuron-methyl, cyprosulfuron-methyl, diclosulam, ethametsulfuron-methyl, ethimethuron-methyl, pyrimsulfuron-methyl, florasulam, flucarbazone-sodium, pyrazasulfuron Amine, sulfuron-methyl, sulfuron-methyl, foramsulfuron-methyl, clopyrazosulfuron-methyl, imazamox-methyl, imazethapyr, imazamox, imazapyr, imidazoquine Phenolic acid, imazethapyr, imazasulfuron, iodosulfuron (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5- Triazin-2-yl)amino]carbonyl]benzenesulfonamide), methylsulfuron-methyl, bis-ether-chloropyrazosulfuron-methyl (3-chloro-4-(5,6-dihydro-5- Methyl-1,4,2-diazin-3-yl)-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole -5-sulfonamide), sulfentrazone, metsulfuron-methyl, nicosulfuron, epoxysulfuron-methyl, penoxsulam, flurimsulfuron-methyl, propoxysulfuron-sodium , Promethazone-methyl (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyrid oxazine-3-sulfonamide), flusulfuron-methyl, pyrazosulfuron-ethyl, saflufenacil, cyclazone, nob methyl ether, pyrithiocarb-sodium, rimsulfuron-methyl, rimsulfuron-methyl -methyl, sulfensulfuron-methyl, thifensulfuron-methyl, thifensulfuron-methyl, flucarbazone-methyl (N-[2-[(4,6-dimethoxy-1,3,5-tri oxazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triflusulfuron-methyl, tribenuron-methyl, trifloxysulfuron-methyl (including the sodium salt), flusulfuron-methyl and triflumesulfuron-methyl.

"ACCase inhibitors" (b3) are chemical compounds that inhibit acetyl-CoA carboxylase, the enzyme responsible for catalyzing the early steps of lipid and fatty acid synthesis in plants. Lipids are a major component of cell membranes, without which new cells cannot be made. Inhibition of acetyl-CoA carboxylase and subsequent lack of lipid production leads to loss of cell membrane integrity, especially in actively growing regions such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die. Examples of ACCase inhibitors include motifen, butoxycyclone, clethodim, clodinafop-propargyl, clodin, cyhalofop, diclofop, fenoxaprop, fluazifop, chlorpyrifos Proxaprop, pinoxaden, cyclazone, oxaclofate, quizalofop, sethoxydim, dexaprop, and oximazone, including decomposed forms such as fenoxaprop-p-ethyl, fluazifop-p-methyl , halofop-p-p, and quizalofop-p-ethyl, and ester forms such as clodinafop-propargyl, cyhalofop-butyl, halofop-methyl, and fenoxaprop-p-p-ethyl.

Auxins are plant hormones that regulate the growth of many plant tissues. "Auxin mimetics" (b4) are chemical compounds that mimic the plant growth hormone auxin, thus causing uncontrolled and disordered growth and consequent plant death in susceptible species. Examples of auxin mimetics include cypromic acid (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyrid , Ethyl Methazolin, Methazone, Chlorophosphate, Chloroformamide, Clopyralid, Dicamba, 2,4-D, 2,4-DB, Dipropionic Acid, Chlorfluroxypyroxy Acetic acid, halopyridine (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid), halopyridine methyl (4- Amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid methyl ester), MCPA, MCPB, 2-methyl-4-chloropropionic acid, toxic Aramam, quinclorac, quinclorac, 2,3,6-TBA, triclopyr, and 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy Phenyl)-5-fluoro-2-pyridinecarboxylic acid methyl ester.

"EPSP synthase inhibitors" (b5) are chemical compounds that inhibit the enzyme, 5-enol-pyruvylshikimate-3-phosphate synthase, which involves aromatic amino acids such as tyrosine, tryptophan and Synthesis of phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant leaves and translocate in the phloem to the growing point. Glyphosate is a relatively non-selective post-emergence herbicide belonging to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimethylsulfonium (otherwise known as glufosinate).

"Photosystem I electron diverter" (b6) is a chemical compound that accepts electrons from Photosystem I and generates hydroxyl radicals after several cycles. These free radicals are extremely reactive and readily damage unsaturated lipids, including membrane fatty acids and chlorophyll. This disrupts the integrity of cell membranes, making cells and organelles "leaky," leading to rapid wilting and drying of leaves and eventually plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

"PPO inhibitors" (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, which rapidly leads in plants to the formation of highly reactive compounds that disrupt cell membranes, resulting in extracellular sap. Examples of PPO inhibitors include acifluorfen-sodium, mefentrazone, bimeflumezone, fenflufen, fluprofen-methyl, mefentrazone, triaflufen-ethyl, methoxyfluben, indole Dufenpyr, Profentrafen, Flupyrafen, Fluoxalic acid, Propyril flufen, Acecarboxyflufen, Flufenoxate, Fomesafen, Halosafen, Milk Fluorine Ling, propargyl oxadiazone, oxadiazole, ethoxyfluorfen, cyclopentaclomazone, flufenacet, bisendenil, metazachlor, saflufenacil, sulfentrazone, thiazide Dimefenacet, tiafenacil (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl )-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alanine ethyl ester) and 3-[7-fluoro-3,4-di Hydrogen-3-oxo-4-(2-propan-1-yl)-2H-1,4-benzoxazin-6-yl]dihydro-1,5-dimethyl-6-thio- 1,3,5-Triazine-2,4(1H,3H)-dione.

A "GS inhibitor" (b8) is a chemical compound that inhibits the activity of glutamine synthase, the enzyme used by plants to convert ammonia to glutamine. As a result, ammonia builds up and glutamine levels decrease. Plant damage may occur due to the combined effect of ammonia toxicity and the lack of amino acids required for other metabolic processes. GS inhibitors include glufosinate and its esters and salts, such as glufosinate-ammonium and other glufosinate derivatives, glufosinate-P((2S)-2-amino-4-(hydroxymethylphosphinyl)butyl acid) and bilagrass.

"VLCFA elongase inhibitors" (b9) are herbicides with various chemical structures that inhibit elongase. Elongase is one of the enzymes located in or near the chloroplast that is involved in the biosynthesis of VLCFAs. In plants, very long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide pollen grain stability. Such herbicides include acetochlor, alachlor, saprophos, butachlor, mefentrachlor, dimetholachlor, xylenolachlor, fenoxasulfone, fenoxasulfone (3-[[(2,5 -dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), tetramen, flufenacet, Indoxalin, mefenazamide, metazachlor, metolachlor, napropamide, napropamide, napropamide-M((2R)-N,N-diethyl-2-(1- naphthylethyloxy)propionamide), metethenamide, dimethafos, pretilachlor, imazachlor, propachlor, roxasulfone, and metmethacetam, including decomposed forms such as metolachlor and chloroacetamide and oxyacetamide.

"Auxin transport inhibitors" (b10) are chemical substances that inhibit auxin transport in plants, such as by binding to auxin carrier proteins. Examples of auxin transport inhibitors include flufenfenpyr, naphthachlor (also known as N-(1-naphthyl)-phthalamylbenzoic acid and 2-[(1-naphthylamino)carbonyl]benzoic acid ).

"PDS inhibitors" (bl 1 ) are chemical compounds that inhibit the carotenoid biosynthetic pathway at the phytoene dehydrogenase step. Examples of PDS inhibitors include flubutyramid, difluzamid, fluridone, flumetrione, furazone, fluroxyfen, and fluflumid.

"HPPD inhibitors" (bl2)) are biosynthetic chemicals that inhibit the synthesis of 4-hydroxy-phenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include bicyclic sulcotrione, metazazone, flumetrione (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoro Methyl)-3-pyridyl]carbonyl]bicyclo[3.2.1]dec-3-en-2-one), fenquinotrione(2-[[8-chloro-3,4-dihydro-4-(4 -methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxaflutole, isoxaflutole, mesotrione, Pyrazole sulfonyl, pyrazolate, benzamconazole, sulcotrione, tefutrione, tembotrione, fenpyrazenone, 5-chloro-3-[(2-hydroxy-6-oxo- 1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methyl Phenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1- Cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-6-oxo- 1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl- N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide, and 2-methyl -3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.

The "HST inhibitor" (b13) disrupts the plant's ability to convert homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include chlorpyrifos, chlorpyridine, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridine-2(1H )-keto, 7-(3,5-dichloro-4-pyridyl)-5-(2,2-difluoroethyl)-8-hydroxypyrrolo[2,3-b]pyrazine-6( 5H)-one and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.

HST inhibitors also include compounds of formula A and B.

Wherein R ^d1 is H, Cl or CF ₃ ; R ^d2 is H, Cl or Br; R ^d3 is H or Cl; R ^d4 is H, Cl or CF ₃ ; R ^d5 is CH ₃ , CH ₂ CH ₃ or CH ₂ CHF ₂ ; and R ^d6 is OH, or -OC(=O)-i-Pr; and R ^e1 is H, F, Cl, CH ₃ or CH ₂ CH ₃ ; R ^e2 is H or CF ₃ ; R ^e3 is H, CH ₃ or CH ₂ CH ₃ ; ^Re4 is H, F or Br; ^Re5 is Cl, CH ₃ , CF ₃ , OCF ₃ or CH ₂ CH ₃ ; ^Re6 is H, CH ₃ , CH ₂ CHF ₂ or C≡CH; ^Re7 is OH, -OC(=O)Et, -OC(=O)-i-Pr or -OC(=O)-t-Bu; and ^Ae8 is N or CH.

Cellulose biosynthesis inhibitor (bl4) inhibits cellulose biosynthesis in certain plants. They are most effective when applied at pre-emergence or early emergence on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include zoklax, dichonil, flufenazole, indachlor (N ² -[(1R,2S)-2,3-dihydro-2,6-dihydro methyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxachlor and triazinflufen.

Other herbicides (b15) include herbicides that act via a number of different modes of action, such as mitotic disruptors (e.g. wheatgrass fluorine-M-methyl and wheatgrass fluorine-M-isopropyl), organic arsenic-containing compounds (e.g. DSMA and MSMA), 7,8-dihydropteroic acid synthesis inhibitors, chloroplast isoprenoid synthesis inhibitors and cell wall biosynthesis inhibitors. Other herbicides include those that have an unknown mode of action or do not fall into the specific classes listed in (b1) to (b14) or act by a combination of the modes of action listed above. Examples of other herbicides include acenifen, orifen, acetap, bromobutyramid, cycloheptafen, clomazone, benuuron, cyclopyrimorate (6-chloro-3-(2-cyclopropyl -6-Methylphenoxy)-4-Pyridazinyl 4-Morpholine Carboxylate), Diuron, Yeyanhu, Ethoxybenz, Fumauron, Azaclodin, Adjust Phosphine, Amino Ammonium Formyl Phosphonate Ethyl Ammonium Salt, Dipyron, Sabolon, Trifenyl (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1, 5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metabam, triauron-methyl, oleic acid , oxazicone, nonanoic acid, barnyard and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-( 3-methyl-2-thienyl)isoxazole.

"Herbicide safeners" (b16) are substances added to herbicide formulations to eliminate or reduce the phytotoxic effects of herbicides on certain crops. These compounds protect crops from herbicide damage, but generally do not prevent the herbicide from controlling undesired vegetation. Examples of herbicide safeners include, but are not limited to, acetoxazone, cloquinone, benuuron, acetamide, cyprosulfonamide, dimethuron, dichloropropenamide, dicyclonon, diphenhydrazol, cloxazone- Ethyl, oxalazine, oxalan, fluroxyme, oxazole, isoxadifen-ethyl, pyrazole oxalic acid-diethyl, 4-chlorophenylmethyl carbamic acid, herbicide Ketones, naphthalic anhydride, oxalanil, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloro (Methyl)-sulfonyl]-benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxo Hetero-4-azospiro[4.5]decane (MON 4660).

Compounds of formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. Compounds of Formula 1 can be prepared using one or more of the following methods and modifications as described in Schemes 1-12. Unless otherwise specified, the definitions of A, R ¹ , Q ¹ , J ¹ , R ² , Q ² , J ² , B, LG, and R ^a in the compounds of formula 1-24 are as defined above in the detailed description. Compounds of Formulas 1a-1h and 4a-4b are various subsets of compounds of Formulas 1 and 4, and all substituents of Formulas 1a-1h and 4a-4b are as defined above for Formulas 1 and 4 unless otherwise indicated.

As shown in Scheme 1, compounds of formula 1a (i.e., compounds of formula 1 wherein X is R ¹ , Y is -Q ¹ -J ¹ and Q ¹ is carbonyl) can be obtained by using general methods well known to those skilled in the art Prepared by oxidation of compounds of formula 1b (ie, compounds of formula 1 wherein X is R ¹ , Y is -Q ¹ -J ¹ and Q ¹ is CH(OH)) using a variety of reagents. Examples of these methods are described in the following references and those cited therein; Tetrahedron 2013, 69, 5568-5972; Eur. J. Org. Chem. 2014, 781-787 and Burke, SD ed., Handbook of Reagents for Organic Synthesis , Oxidizing and Reducing Agents; John Wiley & Sons, Chichester, UK, 1999. The simplest procedure uses commercially available activated manganese _dioxide (Mn02) in refluxing toluene under an oxygen or nitrogen atmosphere. The amount of activated manganese dioxide can range from substoichiometric to excess.

plan 1

As shown in Scheme 2, compounds of formula 1c (i.e., compounds of formula 1, wherein X is R ¹ , Y is Q ¹ -J ¹ and Q ¹ is CH ₂ ) can be obtained by using general methods well known to those skilled in the art Prepared by reducing the compound of formula 1b using a variety of reagents. Examples of these methods are described in the following references and those cited therein; Tetrahedron Lett. 2001, 42, 831-833. A particularly applicable method is the use of hydrogen iodide generated from hypophosphorous acid (H ₃ PO ₂ ) and iodine in the temperature range from 40° C. to reflux, preferably in acetic acid as solvent.

Scenario 2

As shown in Scheme 3, compounds of formula 1b or 1a can be synthesized by adding an organolithium or magnesium reagent of formula 2 to a carbonyl group comprising a compound of formula 3 in a solvent such as tetrahydrofuran at a temperature ranging from -78 °C to room temperature preparation. Compounds of formula 2 are commercially available or can be prepared by methods known in the art.

Option 3

As shown in Scheme 4, compounds of formula 1e-1g (i.e. compounds of formula 1 wherein X is R ¹ , Y is -Q ¹ -J ¹ ; and Q ¹ is O for 1e; Q for 1f ¹ is S and for 1 g Q ¹ is NR ⁶ ) can be dissolved in solvents such as dimethylsulfoxide, N,N-dimethylformamide in the presence of bases such as sodium hydride, cesium carbonate or potassium tert-butoxide Prepared by reaction of a compound of formula 4 with an oxygen, sulfur or nitrogen nucleophile of formula 5 (ie ethanol, thiol or amine) in , tetrahydrofuran or acetonitrile at temperatures ranging from ambient to reflux.

Option 4

As shown in Scheme 5, compounds of formula 4a (a subset of formula ₄ wherein LG is ^SO2Ra ) can be prepared from compounds of formula 6 using general methods well known to those skilled in the art. For example, the thioalkyl group of formula 6 can be used with various reagents such as 3-chloroperoxybenzoic acid (MCPBA) or potassium persulfate (e.g., ) is oxidized to the corresponding sulfonyl of formula 4a. Typically, these oxidations occur in solvents such as dichloromethane (for MCPBA) or acetone and water (for ) at a temperature ranging from 0°C to ambient temperature. For a comprehensive overview of available methodologies for the oxidation of sulfides, see Larock, RC, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Edition, Wiley-VCH, New York, 1999 and references cited therein.

Option 5

Compounds of formula 6 can be prepared using the reaction sequence described in Aust. J. Chem. 1997, 50, 911, as shown in scheme 6. The reaction sequence starts with a concentrate of an aldehyde of formula 7 with a 2-alkyl-3-thiosemicarbazide of formula 8, followed by alkylation with an alkyl halide (where the alkyl is ^Ra ) to produce an intermediate of formula 9. Ring closure of intermediates of compound formula 9 with iron(III) chloride in acetic acid and water provides compounds of formula 6.

Option 6

As shown in Scheme 7, compounds of formula 3, 6, 4b, and 10 can be prepared by treating compounds of formula 11 with organolithium reagents such as n-butyllithium at a temperature of -78 °C, and with various electrophiles Such as N,N-dimethylformamide, alkyl formate, N,N-dialkylcarbamoyl chloride, dialkyl disulfide, halogenating agent or _CO2 quenching.

Option 7

1,3-Disubstituted 1,2,4-triazoles of formula 11 are commercially available or can be prepared by reaction sequences described in the literature, see eg WO2010/074588 or as shown in Scheme 8. The compound of formula 13 (i.e. commercially available benzamide or heteroaromatic amide) was refluxed in N,N-dimethylformamide dimethyl acetal (DMF-DMA), and then treated with hydrazine monohydrate Work-up and heating to reflux in acetic acid affords the 5-substituted 1,2,4-triazole. It is then treated with a base such as potassium carbonate, triethylamine, sodium hydride or sodium hydroxide and various alkylating agents (i.e., R ¹ X ), preferably alkyl iodide, etc., at a temperature ranging from ambient temperature to the reflux temperature of the solvent. Alkylation of 5-substituted 1,2,4-triazoles primarily on N1 in a solvent such as N,N-dimethylformamide, dimethylsulfoxide or tetrahydrofuran yields compounds of formula 11. Other methods for preparing compounds of formula 11 can be found in Science of Synthesis, Georg Thieme Verlag New York, Category 2: Hetarenes and RelatedRing Systems, Volume 13; Five-Membered Hetarenes with Three or More Heteroatoms by ADMCurtis, Product Category 14:1 , 2,4-Triazoles, 2004, 603–640 and J.Org.Chem. 2011, 76, 1177-1179.

Option 8

As shown in Scheme 9, a compound of formula 1h (ie, a compound of formula 1, wherein X is -Q ² -J ² , and Y is R ² ) is prepared by adding a compound of formula 1h in the presence of a base in a suitable solvent such as acetonitrile, tetrahydrofuran, or N , prepared by nucleophilic substitution by heating a compound of formula 14 in N-dimethylformamide with a base such as potassium carbonate or cesium carbonate, having a compound of formula 15. The reaction is usually carried out at a temperature ranging from room temperature to 110°C.

Option 9

As shown in Scheme 10, the compound of formula 14 can be prepared by the method described in J. Am. Chem. Soc. 2009, 131, 15080-15801. The amidine of formula 16 is combined with phenyl or heteroaromatic nitrile of formula 17 and heated at 120 °C in the presence of a base such as potassium carbonate or cesium carbonate and a catalytic amount of copper(I) bromide in a suitable solvent Such as dimethyl sulfoxide, N,N-dimethylacetamide or N,N-dimethylformamide open in the open to provide compounds of formula 14. Other methods for preparing compounds of formula 14 can be found in Science of Synthesis, Georg Thieme Verlag New York, Category 2: Hetarenes and Related Ring Systems, Volume 13 - Five-Membered Hetarenes with Three or More Heteroatoms by A.D.M. Curtis, Product Category 14 : 1,2,4-Triazoles, 2004, pp. 603–640.

Scheme 10

As shown in Scheme 11, compounds of formula 1h can alternatively be prepared by reaction of 1,2,4-triazole derivatives of formula 18, wherein LG is a leaving group such as SO ₂ R (where R is an alkane radical, haloalkyl, phenyl, or p-tolyl) with a broad range of carbon, nitrogen, oxygen, and sulfur nucleophiles including cyanides, amines, alcohols, and thiols, optionally in the presence of bases and solvents. Typical bases that can be used include sodium hydride, cesium carbonate, potassium carbonate or potassium tert-butoxide. Suitable solvents for this substitution reaction are dimethylsulfoxide, N,N-dimethylformamide, tetrahydrofuran and acetonitrile. The reaction temperature ranges from ambient temperature to the reflux temperature of the solvent.

Scheme 11

Compounds of formula 18 can be prepared by the reaction sequence shown in Scheme 12 below. Compounds of formula 19 (ie, 4H-1,2,4-triazole-3-thiol) are commercially available or can be prepared using methods known in the art. Using an alkylating agent at the 3-position on the thiol atom (i.e. R-LG, where LG is the leaving A group such as halo or sulfonyl) compounds of formula 19 are alkylated to provide intermediates 20. Intermediates of formula 20 are then N-alkylated using the method described in Scheme 9 to give compounds of formula 21 . The compound of formula 21 can be treated with various reagents such as 3-chloroperoxybenzoic acid (MCPBA) or potassium persulfate such as is oxidized to the compound of formula 18. Typically, these oxidations are performed at temperatures ranging from 0 °C to room temperature in solvents such as dichloromethane (for MCPBA) or acetone and water (for ) in. For a comprehensive overview of available methodologies for the oxidation of sulfides, see Larock, RC, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Edition, Wiley-VCH, New York, 1999; and references cited therein.

Scheme 12

Compounds of formula 19 can be prepared by literature methods described in J. Med. Chem. 1994, 37, 125-132 and are shown in Scheme 13 below. Aroyl chlorides of formula 22 can be added to thiosemicarbazides of formula 23 in the presence of a base such as pyridine or triethylamine to form acylated thiosemicarbazides of formula 24. Thiosemicarbazides 24 of formula 24 can be cyclized with bases such as potassium carbonate, triethylamine, sodium hydride or aqueous hydroxide bases to form compounds of formula 19. The synthesis outlined in Scheme 13 is described in steps A and B of Synthesis Example 6.

Scheme 13

The skilled artisan will appreciate that compounds of formula 19 can exist in various tautomeric forms, such as compounds of formulas 19A, 19B and 19C.

The particular tautomer drawn may not be the lowest energy tautomer present based on a number of factors, including variables such as the value of "A" and physical form (ie, solid or dissolved in solution).

Those skilled in the art recognize that various functional groups can be transformed into others to provide different compounds of formula 1 . For a valuable resource showing functional group interconversions in a simple and intuitive manner, see Larock, R.C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd ed., Wiley-VCH, New York, 1999. For example, intermediates used to prepare compounds of Formula 1 may contain aromatic nitro groups, which can be reduced to amino groups and then converted to various halides via reactions well known in the art, such as the Sandmeyer reaction, to provide compounds of Formula 1. compound. In many cases, the above reactions can also be performed in an alternative order.

It is recognized that certain reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be compatible with certain functional groups present in the intermediates. In these cases, the incorporation of protection/deprotection sequences or functional group tautomers into the synthesis will help to obtain the desired product. The use and choice of protecting groups will be apparent to those skilled in the art of chemical synthesis (see eg Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, 2nd Ed.; Wiley: New York, 1991). Those skilled in the art will recognize that in some cases, following the introduction of a given reagent as shown in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of the compound of Formula 1 . Those skilled in the art will also recognize that combinations of steps shown in the schemes above need to be performed in an order different from the specific sequence presented for the preparation of compounds of Formula 1 .

Those skilled in the art will also recognize that compounds of Formula 1 and intermediates described herein can undergo a variety of electrophilic, nucleophilic, free radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following non-limiting examples are illustrative of the invention. The procedures in the following examples show the procedure of each step in the overall synthetic transformation, and the starting materials used in each step are not necessarily prepared by the specific preparative steps whose procedures are described in other examples or procedures. Percentages are by weight except for chromatographic solvent mixtures or unless otherwise indicated. Parts and percentages of chromatographic solvent mixtures are by volume unless otherwise indicated. ^1H NMR spectra are reported in ppm downfield from tetramethylsilane in _CDCl3 unless otherwise indicated; "s" indicates singlet, "d" indicates doublet, "t" indicates triplet, "q" indicates a quartet, "bs" indicates two broad singlets, and "m" indicates a multiplet. The mass spectrum is formed by adding H ⁺ (molecular weight 1) to the molecule by using a combination of liquid chromatography and mass spectrometer (LCMS), observed using atmospheric pressure chemical ionization (AP ⁺ ) or electrospray ionization (ES ⁺ or ES-) Recorded as the molecular weight of the most isotopically abundant precursor ion (M+1) of , or (M-1) formed from the loss of H ⁺ (molecular weight 1) from the molecule.

Synthesis Example 1

Preparation of 4-[[5-ethyl-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl) Methyl)pyridine (compound 1)

Step A: Preparation of 2-trifluoromethyl-pyridin-4-ylmethyl bromide

A solution of 2-trifluoromethyl-pyridin-4-ylmethanol (0.5 g, 2.8 mmol) in 14.0 mL of dichloromethane was stirred under nitrogen atmosphere and cooled to a temperature below 10 °C using an ice-water bath. Phosphorus tribromide (0.76 g, 2.8 mmol) was added and the reaction mixture was stirred at ambient temperature for 16 h. After the reaction was complete, the mixture was poured into ice-water and saturated aqueous sodium bicarbonate solution. The aqueous layer was separated and extracted three times with dichloromethane. The combined organic layers were washed with brine, dried over MgSO ₄ , filtered and concentrated to give the title compound (0.39 g).

¹ H NMR δ 8.71 (d, 1H), 7.71 (s, 1H), 7.52 (d, 1H), 4.46 (s, 2H).

Step B: Preparation of 3-ethyl-5-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazole

Carbonic acid was added to a solution of propionamidine hydrochloride (1.90 g, 17.5 mmol) and α,α,α-trifluoro-p-methylbenzonitrile (2.0 g, 11.7 mmol) in 30 mL of dimethylsulfoxide Cesium (11.4g, 34.9mmol) and copper(I) bromide (0.3g, 1.05mmol), and the mixture was stirred and heated at 120°C for 16h, open in the open. After completion of the reaction, the reaction mixture was cooled and diluted with water, quenched with saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate. The aqueous layer was separated and extracted twice with ethyl acetate. The combined ethyl acetate layers were washed with saturated aqueous EDTA and brine, dried over _MgSO4 and concentrated to afford 1.69 g of a crude solid. The crude solid was dissolved in diethyl ether. The intermediate 4-trifluoromethylbenzamide as a by-product 177 mg was filtered off as a white solid. The filtrate was concentrated and the residue was purified by a 40 g silica gel column eluting with a gradient of 10%, 25%, 50% ethyl acetate in hexanes to afford the title compound as a solid (0.57 g).

¹ H NMR δ 8.20 (d, 2H), 7.69 (d, 2H), 2.90 (q, 2H), 1.42 (t, 3H).

Step C: Preparation of 4-[[5-ethyl-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]-2- (Trifluoromethyl)pyridine

3-Ethyl-5-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazole (the product of Step B) (0.21 g, 0.88 mmol) and 2-(Trifluoromethyl-pyridin-4-yl)methyl bromide (ie the product of step A) (0.23 g, 0.971 mmol) in N,N-dimethylformamide (2.0 mL) Powdered potassium carbonate (0.31 g, 2.21 mmol) was added and the reaction mixture was stirred at ambient temperature for 16 h. The mixture was then diluted with water and diethyl ether and the layers were separated. The aqueous layer was extracted twice with diethyl ether. The organic layers were combined and washed three times with water, dried over _MgSO4 , filtered and concentrated to afford 0.28 g of oil as crude product. The crude product was purified using a 12 g silica gel column eluting with a gradient of 10% to 30% ethyl acetate in hexanes to afford the title compound (0.22 g).

¹ H NMRδ8.72(d,1H), 8.21(d,2H), 7.68(d,2H), 7.53(s,1H), 7.25(d,1H), 5.44(s,2H), 2.79(q, 2H), 1.37(t,3H).

(comparative) synthesis embodiment 2

Preparation of 3-(4-fluorophenyl)-1-methyl-5-[3-(trifluoromethyl)phenoxy]-1H-1,2,4-triazole (Compound 5)

Step A: Preparation of methyl 2-[(4-fluorophenyl)methylene]-1-methylhydrazine carboximide sulfate

A solution of 4-fluorobenzaldehyde (2.5 g, 20 mmol) and 2-methyl-3-thiosemicarbazide (2.12 g, 20.1 mmol) in methanol (100 mL) was stirred at reflux overnight under nitrogen atmosphere. The reaction mixture was then cooled to 0 °C, and iodomethane (15.72 g, 110.8 mmol) was added. The reaction mixture was stirred at room temperature for 3 days. The precipitated white solid was filtered off and dried with vacuum line to afford the title compound (2.2 g).

MS (ES ⁺ ) 225.9 (M+1).

Step B: Preparation of 3-(4-fluorophenyl)-1-methyl-5-(methylthio)-1H-1,2,4-triazole

To methyl 2-[(4-fluorophenyl)methylene]-1-methylhydrazine carboximide sulfate (i.e. the product of step A) (2.2 g, 9.8 mmol) was added dropwise via an additional funnel A solution of acetic acid (60 mL) and water (60 mL) was added to a solution of iron(III) chloride (5.23 g, 32.22 mmol) in water (60 mL). The reaction mixture was heated to reflux for 4h. After the reaction was complete, the reaction mixture was cooled to room temperature. Toluene was added and removed using a rotary evaporator. The residue was neutralized to pH= ₈ with saturated aqueous _NaHCO3 and _Na2CO3 solution. The resulting mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried and concentrated to afford 1.6 g of a solid. The solid was washed with hexane to afford the title compound (0.69g).

¹ H NMR δ 8.40 (m, 2H), 7.09 (t, 2H), 3.80 (s, 3H), 2.74 (s, 3H).

Step C: Preparation of 3-(4-fluorophenyl)-1-methyl-5-(methylsulfonyl)-1H-1,2,4-triazole

3-(4-Fluorophenyl)-1-methyl-5-(methylthio)-1H-1,2,4-triazole (the product of Step B) (0.6 g, 2.60 mmol) was stirred in di Chloromethane (30 mL) solution and cooled to 0°C with an ice-acetone bath. MCPBA (1.5 g, 6.5 mmol) was added to the solution. The reaction mixture was stirred overnight at room temperature. The reaction was diluted with saturated aqueous NaHCO ₃ . The aqueous layer was separated and extracted with dichloromethane. All organic layers were combined and washed with saturated aqueous NaHCO ₃ , brine, dried over MgSO ₄ , and concentrated to afford 0.4 g of a solid. The solid was washed with hexane to afford the title compound (268 mg).

¹ H NMR δ 8.08 (m, 2H), 7.13 (t, 2H), 4.23 (s, 3H), 3.48 (s, 3H).

Step D: Preparation of 3-(4-fluorophenyl)-1-methyl-5-[3-(trifluoromethyl)phenoxy]-1H-1,2,4-triazole

To the N , N-dimethylformamide (0.75 mL) solution was added α,α,α-trifluoro-m-cresol (110 mg, 0.682 mmol) and potassium carbonate (145 mg, 1.05 mmol). After heating the reaction mixture at 100 °C for 5 h, it was cooled to room temperature and allowed to stand for 16 h. The reaction mixture was then diluted with water and diethyl ether. The aqueous layer was separated and extracted with diethyl ether (2x). All organic layers were combined and washed with water (3x), 1N NaOH solution, brine, dried _{over Na2SO4} and concentrated to afford the title compound (190 mg).

¹ H NMR δ 7.97 (m, 2H), 7.69 (s, 1H), 7.61 (d, 1H), 7.48–7.58 (m, 2H), 7.08 (t, 2H), 3.84 (s, 3H).

Synthesis Example 3

Preparation of 4-[[3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl]methyl]-2-(trifluoromethyl)pyridine (compound 13)

Step A: Preparation of N-[(dimethylamino)methylene]-4-fluorobenzamide

A solution of fluorobenzamide (10 g, 71.9 mmol) in DMF-DMA (21.4 g, 180 mmol) was heated at 80 °C for 1 h. The reaction mixture was then cooled down and concentrated to give a white solid. The resulting white solid was washed with hexane to afford the title compound (12.72 g).

¹ H NMR δ 8.63 (s, 1H), 8.30 (m, 2H), 7.07 (t, 2H), 3.21 (s, 3H), 3.19 (s, 3H).

Step B: Preparation of 5-(4-fluorophenyl)-1H-1,2,4-triazole

To a solution of N-[(dimethylamino)methylene]-4-fluorobenzamide (i.e. the product of step A) (12.7 g, 65.5 mmol) in acetic acid was added hydrazine monohydrate (3.6 g, 72 mmol) at room temperature ). After the reaction exothermed to 90 °C, the reaction mixture was heated at 120 °C for 2 h. The reaction was then cooled down to room temperature and concentrated. Toluene was added to the residue and then concentrated to provide an oil. The solid was triturated from water and washed with hexanes to afford the title compound (10.6 g).

¹ H NMR (DMSO-d ₆ ) δ 8.45 (s, 1H), 8.05 (m, 2H), 7.32 (m, 2H).

Step C: Preparation of 3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazole

To a solution of 5-(4-fluorophenyl)-1H-1,2,4-triazole (i.e. the product of Step B) (5.0 g, 30.65 mmol) in N,N-dimethylformamide was added potassium carbonate (10.6g, 76.6mmol) and iodomethane (15.2g, 107mmol). The reaction mixture was stirred at ambient temperature for 16 h. The reaction was then diluted with water and diethyl ether. The aqueous layer was separated and extracted with diethyl ether (2x). The organic layers were then combined and washed with water (3x), brine, concentrated, and the residue redissolved in dichloromethane, dried over MgSO ₄ , filtered and concentrated to provide a solid. The solid was washed with hexane to obtain the title compound (1.16 g).

¹ H NMR δ 8.07 (m, 2H), 8.04 (s, 1H), 7.12 (m, 2H), 3.96 (s, 3H).

Step D: Preparation of 3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazole-5-carbaldehyde

1-Methyl-3-(4-fluorophenyl)-1H-1,2,4-triazole (i.e. the product of Step C) (1.35 g, 7.62 mmol) was injected via a syringe through a septum at −78 °C A solution of tetrahydrofuran (15 mL) was added to a 2.5M solution of n-butyllithium in hexane (3.35 mL, 8.38 mmol), keeping the temperature below -50 °C. The reaction mixture was stirred at -78 °C for 2 h. N,N-Dimethylformamide (1.1 mL, 13.71 mmol) was added and the reaction was allowed to warm to 0° C., then quenched with saturated aqueous NH ₄ Cl solution (25 mL). The reaction mixture was extracted with ethyl acetate (3x). All organic layers were combined and washed with brine, dried over MgSO ₄ , filtered and concentrated to afford 1.38 g of solid. The solid was washed with hexane to obtain the title compound (1.01 g).

¹ H NMR δ 10.04 (s, 1H), 8.11 (m, 2H), 7.16 (t, 2H), 4.25 (s, 3H).

Step E: Preparation of α-[3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl]-2-(trifluoromethyl)-4- pyridinemethanol

A solution of 4-iodo-2-(trifluoromethyl)pyridine (0.49 g, 1.82 mmol) in tetrahydrofuran (3 mL) was cooled to 0 °C and 1.3 M A solution of propylmagnesium chloride and lithium chloride in tetrahydrofuran (1.55 mL, 1.99 mmol) was added. The reaction mixture was stirred at room temperature for 1 h. The reaction mixture was then cooled to -78°C and 3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazole-5-carbaldehyde, also cooled to -78°C prior to the addition was added (ie, the product of Step D) (0.34 g, 1.65 mmol) in 3 mL THF. The reaction mixture was allowed to warm to ambient temperature and quenched with saturated aqueous _NH4Cl . The resulting mixture was extracted with ethyl acetate (2x). The combined organic layers were washed with brine, dried over MgSO ₄ , filtered and concentrated to afford 0.57 g of solid residue. The residue was purified by 12 silica gel column eluting with 30% to 32% ethyl acetate in hexanes to afford the title compound (0.31 g).

¹ H NMRδ8.77(d,1H),8.02(m,2H),7.81(s,1H),7.52(d,1H),7.14(t,2H),6.17(s,1H),4.06(bs, 1H), 3.72(s, 3H).

Step F: Preparation of 4-[[3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl]methyl]-2-(trifluoromethyl base) pyridine

To α-[3-(4-fluorophenyl)-1-methyl-1H-1,2,4-triazol-5-yl]-2-(trifluoromethyl)-4-pyridinemethanol (ie To a solution of the product of Step E) (0.25 g, 0.709 mmol) in acetic acid (3 mL) was added iodine (360 mg, 1.42 mmol) and then hypophosphorous acid (187 mg, 2.83 mmol). The reaction mixture was heated at 110 °C for 16 h. The next day more iodine (360mg) and hypophosphorous acid (187mg) were added and heating was continued at 110°C for 16h. The reaction was cooled to 0 °C and diluted with 1 N aqueous NaOH and saturated aqueous NaHCO ₃ solution. The reaction mixture was extracted with ethyl acetate (3x). The combined organic layers were washed with brine, dried over MgSO ₄ , filtered and concentrated to give 0.12 g of an oil. The oil was purified by a 12 g silica gel column eluting with 10% ethyl acetate in dichloromethane to give the title compound (60 mg).

¹ H NMRδ8.70(d,1H),8.05(m,2H),7.61(s,1H),7.40(d,1H),7.12(t,2H),4.28(s,2H),3.83(s, 3H).

Synthesis Example 4

Preparation of 4-[[5-ethoxy-3-(4-fluorophenyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine Pyridine (Compound 8)

Step A: Preparation of 4-[[3-(4-fluorophenyl)-5-(methylthio)-1H-1,2,4-triazol-1-yl]methyl]-2-(tri Fluoromethyl)pyridine

To a solution of 5-(4-fluorophenyl)-4H-1,2,4-triazole-3-thiol (2.5 g, 12.8 mmol) in N,N-dimethylformamide (30 mL) was added the powder Potassium carbonate (4.45 g, 32.2 mmol) was added followed by methyl iodide (2.0 g, 14.10 mmol). The mixture was stirred at ambient temperature for 16 h. The reaction was then diluted with water and diethyl ether. The aqueous layer was separated and extracted with diethyl ether (2x). The combined organic layers were washed with water (2x), brine and concentrated. The resulting residue was then dissolved in ethyl acetate and dried over _MgSO4 , filtered and concentrated. The resulting residue was purified on a 40 g silica gel column eluting with 10% to 20% ethyl acetate in hexanes to afford 2.8 g of a solid. The solid was washed with hexane, and filtered to obtain the title compound (1.6 g).

¹ H NMR δ 8.10 (m, 2H), 7.26 (t, 2H), 2.68 (s, 3H).

Step B: Preparation of 3-(4-fluorophenyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine

To 3-(4-fluorophenyl)-5-(methylthio)-1H-1,2,4-triazole (i.e. the product of step A) (1.6g, 7.65mmol) and 2-trifluoromethyl -Pyridin-4-ylmethyl bromide (i.e. the product of step A in Synthetic Example 1) (2.3g, 8.4mmol) in N,N-dimethylformamide solution was added powdered potassium carbonate (2.6g, 19.12 mmol). The mixture was stirred at ambient temperature for 16 h. The reaction was then diluted with water and diethyl ether. The aqueous layer was separated and extracted with diethyl ether (2x). The combined organic layers were washed with water (2x), brine, dried _{over Na2SO4} , filtered and concentrated to give 3.3g of an oil. The oil was purified by a 40 g silica gel column eluting with 20% to 40% ethyl acetate in hexanes to afford the title compound (1.81 g) as a white solid.

¹ H NMRδ8.72(d,1H),8.06(m,2H),7.59(s,1H),7.33(d,1H),7.12(t,2H),5.35(s,2H),2.78(s, 3H).

Step C: Preparation of 4-[[3-(4-fluorophenyl)-5-(methylsulfonyl)-1H-1,2,4-triazol-1-yl]methyl]-2- (Trifluoromethyl)pyridine

To 3-(4-fluorophenyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine (i.e. the product of Step B) at room temperature ( 0.5 g, 1.4 mmol) in dichloromethane (9.6 mL) was added MCPBA (0.78 g, 3.4 mmol) and stirred overnight. The reaction mixture was diluted with saturated aqueous NaHSO ₃ and dichloromethane. The aqueous layer was separated and extracted with dichloromethane. All layers were combined and washed with saturated aqueous NaHSO ₃ (1x), aqueous NaHCO ₃ (2x), brine, dried over magnesium sulfate, filtered and concentrated to give 0.57 g of a white solid. The white solid was washed with hexane to obtain the title compound (418 mg).

¹ H NMRδ8.78(d,1H),8.19(m,2H),7.74(s,1H),7.52(d,1H),7.15(t,2H),5.79(s,2H),3.49(s, 3H).

Step D: Preparation of 4-[[5-ethoxy-3-(4-fluorophenyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoro methyl)pyridine

After adding 4-[[3-(4-fluorophenyl)-5-(methylsulfonyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethane Sodium hydride (60% dispersion in oil) (22 mg, 0.55 mmol) was dissolved in ethanol (1.5 mL) and stirred for about fifteen minutes. The reaction mixture was heated to 65 °C for 3 h before the reaction was allowed to stand at ambient temperature for 16 h. The reaction was then diluted with water and a white solid precipitated. The white solid was isolated by filtration and rinsed well with water followed by hexanes. The solid was dried in vacuo to obtain the title compound (76mg).

¹ H NMRδ8.71(d,1H),7.99(m,2H),7.60(s,1H),7.37(d,1H),7.10(t,2H),5.22(s,2H),4.58(t, 2H), 1.46(t,3H).

Synthesis Example 5

Preparation of [1-ethyl-3-(4-fluorophenyl)-1H-1,2,4-triazol-5-yl][2-(trifluoromethyl)-4-pyridyl]methanol Ketone (compound 19)

Step A: Preparation of [1-ethyl-3-(4-fluorophenyl)-1H-1,2,4-triazol-5-yl][2-(trifluoromethyl)-4-pyridine Pyridyl]methanone

α-[1-Ethyl-3-(4-fluorophenyl)-1H-1,2,4-triazol-5-yl]-2-(trifluoromethyl)-4-pyridinemethanol (with Prepared in a similar manner to that described above in the Examples above, 3200 mg, 0.55 mmol) and manganese(IV) oxide (1.8 g, 21 mmol) were combined and the resulting mixture was heated at the reflux temperature of the solvent for 3 h. The mixture was cooled and allowed to stand at ambient temperature overnight. pass Filter the mixture through a pad of celite filter aid and rinse well with ethyl acetate. The filtrate was concentrated to afford 0.17 g of an oil which was purified by silica gel chromatography using a gradient of 10-30% ethyl acetate in dichloromethane to afford 30 mg of the title compound as a solid.

¹ H NMRδ9.01(d,1H),8.71(s,1H),8.57(d,1H),8.13(m,2H),7.17(t,2H),4.73(q,2H),1.62(t, 3H).

Synthesis Example 6

Preparation of 4-[[5-ethoxy-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]-2-(tri Fluoromethyl)pyridine (compound 35)

Step A: Preparation of Benzoic Acid, 4-(Trifluoromethyl), 2-(Aminothiocarbonyl)hydrazide

Thiosemicarbazide (1.99 g, 21.79 mmol) was dissolved in 20 mL of pyridine under nitrogen atmosphere. The reaction mixture was cooled using an ice-water bath. 4-(Trifluoromethyl)benzoyl chloride (5 g, 23.97 mmol) was added dropwise via addition funnel, keeping the temperature below 5 °C. The resulting yellow suspension was stirred at ambient temperature for 16 h. The reaction mixture was diluted with excess dichloromethane, and then concentrated under reduced pressure to obtain a solid. Deionized water was added directly to the residue. The solid was then filtered off and rinsed well with deionized water followed by hexane. The solid was air dried to obtain 7.64 g of the title compound.

¹ H NMR(DMSO)δ9.41(bs,1H),8.64(bs,1H),8.08(d,2H),7.93(m,1H),7.88(d,2H),7.76(bs,1H), 8.50(t,1H).

Step B: Preparation of 1,2-dihydro-5-[4-(trifluoromethyl)phenyl]-3H-1,2,4-triazole-3-thione

To 1.6 g of benzoic acid, 4-(trifluoromethyl), 2-(aminothiocarbonyl)hydrazide (i.e. the product obtained in step A, 6.08 mmol) was added 1.0 mL of 1N NaOH containing aqueous solution. The mixture was heated to the reflux temperature of the solvent for 2.5 h. The mixture was cooled to ambient temperature and acetic acid was added, followed by deionized water. The resulting precipitate was filtered off and the solid was rinsed with deionized water followed by hexane. The solid was air dried to afford 2.84 g of the title compound as a white solid.

¹ H NMR (DMSO) δ 8.13(d,2H), 7.91(d,2H).

Step C: Preparation of 5-(methylthio)-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazole

1,2-Dihydro-5-[4-(trifluoromethyl)phenyl]-3H-1,2,4-triazole-3-thione (i.e., from step B above, product, 2.8 g, 11.42 mmol) was dissolved in 30 mL of N,N-dimethylformamide. Powdered potassium carbonate (3.94 g, 28.54 mmol) was added followed by iodomethane (1.78 g, 12.56 mmol). The resulting mixture was stirred overnight at ambient temperature. The reaction was diluted with deionized water and diethyl ether. The layers were separated, and the layer was extracted with diethyl ether (3X). The combined organic layers were washed three times with deionized water and once with brine. The organic layer was dried over sodium sulfate, filtered and concentrated to obtain 4.02 g of solid. The solid was suspended in hexane, and the mixture was filtered to afford a white solid (1.95 g).

¹ H NMR δ 8.18 (d, 2H), 7.71 (d, 2H), 2.74 (s, 3H).

Step D: Preparation of 4-[[5-(methylthio)-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methanol Base]-2-(trifluoromethyl)pyridine

5-(Methylthio)-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazole (i.e. the product obtained in step C above, 1.32 g, 5.08mmol) was dissolved in 16mL of N,N-dimethylformamide. To this mixture was added powdered potassium carbonate (1.75 g, 12.69 mmol), followed by 2-trifluoromethyl-pyridin-4-ylmethyl bromide (i.e. the product of Example 1, step A, 1.34 g, 5.58 mmol). The resulting mixture was stirred at ambient temperature for 16 h. The reaction mixture was diluted with deionized water and diethyl ether. The aqueous layer was separated and extracted three times with diethyl ether. The combined organic layers were washed three times with deionized water, followed by brine. The organic layer was dried over sodium sulfate, filtered and concentrated to obtain 2.81 g of an oil. Purification by silica gel column chromatography using a gradient of hexane to 20% ethyl acetate in hexane gave 1.82 g of the title compound as a yellow solid. The yellow solid was collected from hexane and diethyl ether to afford the title compound (1.22 g) as a solid.

¹ H NMRδ8.72(d,1H),8.20(d,2H),7.69(d,2H),7.59(s,1H),7.34(d,1H),5.38(s,2H),2.79(s, 3H).

Step E: Preparation of 4-[[5-(methylsulfonyl)-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl] Methyl]-2-(trifluoromethyl)pyridine

4-[[5-(methylthio)-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]-2-( Trifluoromethyl)pyridine (ie the product obtained in step D, 1.22 g, 2.92 mmol) was dissolved in 30 mL of acetone and 7 mL of deionized water while stirring under nitrogen atmosphere. added at ambient temperature (potassium peroxypersulfate, 2.7g, 4.37mmol) and stirred for 16h. add additional (2.0 g) and the reaction mixture was stirred for 3 h. The reaction mixture was concentrated under reduced pressure, then diluted with deionized water and ethyl acetate. The aqueous phase was separated and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and concentrated to give 1.47 g of a solid. The solid was purified by silica gel column chromatography using a 20 to 40% gradient of ethyl acetate in hexanes to afford 0.85 g of the title compound as a solid. The solid was filtered from hexane and diethyl ether to afford 564 mg of the title compound.

¹ H NMR δ 8.77(d,1H), 8.21(d,2H), 7.70-7.77(s&d,3H), 7.52(d,1H), 5.83(s,2H), 3.52(s,3H).

Step F: Preparation of 4-[[5-ethoxy-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]- 2-(Trifluoromethyl)pyridine

Sodium hydride (60% in mineral oil, 50 mg, 0.67 mmol) was dissolved in 1.5 mL of ethanol under nitrogen atmosphere. The mixture was stirred at room temperature for about 15 min, after which 4-[[5-(methylsulfonyl)-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazole -1-yl]methyl]-2-(trifluoromethyl)pyridine (ie the product obtained in Step E, 0.20 g, 0.44 mmol) was added as 1.5 mL of a solution in N,N-dimethylformamide. The resulting mixture was heated at 65 °C for 2 h. The cooled reaction mixture was diluted with deionized water. The precipitated solid was filtered and rinsed well with deionized water followed by hexane. The solid was air dried to obtain 57 mg of the title compound.

¹ H NMRδ8.72(d,1H),8.13(d,2H),7.69(d,2H),7.60(s,1H),7.38(d,1H),5.25(s,2H),4.60(q, 2H), 1.46(t, 3H).

The compounds in Tables 1 to 278 below can be prepared by the procedures described herein as well as methods known in the art. Notably, Tables 1 to 75, 109 to 226, and 255 to 278. The following abbreviations are used in subsequent tables: n for normal, i for iso, Me for methyl, Et for ethyl, Pr for propyl, Bu for butyl, i-Pr for isopropyl, n-Bu for normal Butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, -CN means cyano, Py means pyridyl, _-NO2 means nitro, _CF3 means trifluoromethane group, Ph represents phenyl and S(O) ₂ Me represents methylsulfonyl. Each value of J in the table below refers back to the respective value of J listed below. Of note is the value of J, where J is selected from J-2a, J-2b, J-2c, J-10a, J-17a, J-17b, J-18a, J-20a, J-22a, J- 29a and J-33a.

Table 1

J ¹ =J-2a, Q ¹ =O, R ¹ =CH ₃

The present disclosure also includes Tables 2-160. Each table is constructed in the same manner as Table 1 above, except that the row headings in Table 1 (i.e., "J ¹ =J-2a, Q ¹ =O, R ¹ =CH ₃ ") are replaced by The corresponding row headings are replaced. For example, in Table 2, the row heading is "J1 is J ^- 2a, Q1 is O and R1 is Et", and ^A is as defined in Table ¹ .

Form 161

Table 161 is constructed in the same manner as Table 1, except that the structures and row headings in Table 1 are replaced by the structures and row headings below. The values of variable A are as defined in Table 1.

J ² =J-2a, Q ² =CH ₂ , R ² =CH ₃

The present disclosure also includes Tables 162-278. Each table is constructed in the same manner as Table 161 above, except that the row headings in Table 161 (i.e., "J ² =J-2a, Q ² =CH ₂ , R ² =CH ₃ ") are shown below The corresponding row headers for the . For example, the row headings in Table 162 are "J ² =J-2a, Q ² =CH ₂ , R ² =Et" and A is as defined in Table 1 .

Formulation/Application

The compounds of the present invention are generally useful as herbicidally active ingredients in compositions, i.e. formulations, which have at least one additional component acting as a carrier selected from the group consisting of surfactants, solid diluents and liquid thinner. Formulation or composition ingredients are selected to suit the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.

Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and/or suspoemulsions), and the like, which may optionally be thickened into gelled glue. The general types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates and suspoemulsions. The general types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

General types of solid compositions are dusts, powders, granules, pellets, pellets, pastilles, tablets, filled films (including seed coatings), etc., which may be water-dispersible ("wettable") or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively, the entire active ingredient formulation can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations. High-strength compositions are mainly used as intermediates for further formulations.

Sprayable formulations are generally dispersed in a suitable medium prior to spraying. Such liquid and solid preparations are formulated so as to be readily dilutable in a spray medium, usually water, but occasionally another suitable medium such as an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes may range from about one liter to several thousand liters per hectare, but more typically range from about ten liters to several hundred liters per hectare. Sprayable formulations may be mixed in a tank with water or another suitable medium for foliar treatment by air or ground application, or applied to the plant's growing medium. Liquid and dry formulations can be dosed directly into drip irrigation systems, or dosed into furrows during planting.

Such formulations will generally contain effective amounts of active ingredient, diluents and surfactants in the following approximate ranges, totaling up to 100% by weight.

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite, and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silicon dioxide, talc, mica , diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluent and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey.

Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethylsulfoxide, N-alkylpyrrolidones (e.g., N-methyl pyrrolidone), alkyl phosphates (e.g. trimethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g. white mineral oil, n-paraffin , isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatics, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2 - Heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, acetic acid Tridecyl esters and isobornyl acetate, other esters such as alkylated lactates, dibasic esters, alkyl and aryl benzoates and gamma-butyrolactone, and may be linear, branched , saturated or unsaturated alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, Isostearyl Alcohol, Cetyl Alcohol, Lauryl Alcohol, Tridecyl Alcohol, Oleyl Alcohol, Cyclohexanol, Tetrahydrofurfuryl Alcohol, Diacetone Alcohol, Cresol, and Benzyl Alcohol. Liquid diluents also include glycerides of saturated and unsaturated fatty acids (usually C ₆ -C ₂₂ ), such as oils of seeds and fruits of plants (for example, olive oil, castor oil, linseed oil, sesame oil, corn (corn) oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), fats of animal origin (such as tallow, lard, lard, cod liver oil, fish oils), and mixtures thereof. Liquid diluents also include alkylated (eg, methylated, ethylated, butylated) fatty acids, which fatty acids can be obtained by hydrolysis of glycerides from vegetable and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the invention generally comprise one or more surfactants. When added to a liquid, surfactants (also referred to as "surfactant agents") typically alter, most typically lower, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, surfactants can act as wetting agents, dispersants, emulsifiers or defoamers.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alcohol alkoxylates, such as those based on natural alcohols and synthetic alcohols (which may be branched or linear) and composed of alcohols and ethylene oxide, epoxy Alcohol alkoxylates prepared from propane, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethyl Oxylated soybean oil, castor oil and rapeseed oil; alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and dodecylphenol ethoxylate Alkylphenol ethoxylates (obtained from phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers obtained from ethylene oxide or propylene oxide and terminal Trans-block polymers with blocks derived from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters and polyethoxylated glycerol fatty acid esters); other sorbitan derivatives such as sorbitan esters; polymeric surfactants , such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acids esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives substances such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphoric esters such as those of alcohol alkoxylates, of alkylphenol alkoxylates and benzene Phosphate esters of vinylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; ethoxylated alkylphenols sulfates and sulfonates of alcohols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyl taurates; benzene, isopropyl, toluene, Xylene and sulfonates of dodecylbenzene and tridecylbenzene; sulfonates of polycondensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; sulfonates of petroleum fractions; sulfosuccinamic acid salts; and sulfosuccinates and their derivatives, such as dialkylsulfosuccinates.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkylpropylenediamines, tripropylenetriamines, and dipropylenetetramines, and ethoxylated amines, Ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts, such as quaternary salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides, such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants. Nonionic, anionic, and cationic surfactants and their recommended uses are described in several published references, including McCutcheon's Emulsifiers and Detergents, The Manufacturing Confectioner Publishing Co., a McCutcheon Division, North American and International Annual Editions; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York York, 1987.

The compositions of the present invention may also contain formulation auxiliaries and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered to function as solid diluents, liquid diluents or surfactants). Such formulation aids and additives control: pH (buffers), foaming during processing (defoamers such as polyorganosiloxanes), settling of active ingredients (suspension agents), viscosity (thixotropic thickening agents), microbial growth in containers (antimicrobial agents), product freezing (antifreeze agents), color (dye/pigment dispersions), elution (film formers or adhesives), evaporation (anti-evaporation agents), and others formulation properties. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Volume 2: Functional Materials, North American and International Yearbook Editions, published by The Manufacturing Confectioner Publishing Co., a McCutcheon Division; and PCT Publication WO 03/024222.

The compound of Formula 1 and any other active ingredient are generally incorporated into the compositions of the invention by dissolving the active ingredient in a solvent or by triturating the active ingredient in a liquid or dry diluent. Solutions comprising emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of the liquid composition intended to be used as an emulsifiable concentrate is water-immiscible, an emulsifier is usually added to emulsify the solvent containing the active ingredient on dilution with water. Active ingredient slurries having a particle size of up to 2,000 μm may be ground using a media mill to obtain particles having an average diameter below 3 μm. Aqueous slurries can be prepared as finished suspension concentrates (see, eg, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations generally require a dry milling process, which produces average particle sizes in the range of 2 μm to 10 μm. Dusts and powders can be prepared by blending, and usually by grinding, such as with a hammer mill or fluid energy mill. Granules and pellets can be prepared by spraying the active material onto preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration" (Chemical Engineering, Dec. 4, 1967, pp. 147–48), Perry, Chemical Engineer's Handbook, 4th edition (McGraw-Hill, New York, 1963, pp. 8–57, and following page) and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared according to the teachings of U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets may be prepared according to the teachings of U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Membranes can be prepared according to the teachings in GB 2,095,558 and U.S. 3,299,566.

For further information on the field of formulation, see "The Formulator's Toolbox-Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience by T.S. Woods, The Food-Environment Challenge, edited by T. Brooks and T.R. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry , The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, column 6, lines 16 to 7, line 19 and examples 10-41; U.S. 3,309,192, column 5, lines 43 to 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. 2,891,855, column 3, line 66 to column 5, line 17 and Examples 1-4; Klingman's Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96; Hance et al.'s Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford , 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the following examples, all percentages are by weight and all formulations are prepared in conventional manner. Compound numbers refer to compounds in Index Tables A-B. Without further elaboration, it is believed that one skilled in the art, using the preceding description, can utilize the present invention to its fullest extent. The following non-limiting examples are illustrative of the invention. Percentages are by weight unless otherwise indicated.

Example A

High Strength Concentrate

Compound 1 98.5%

Silica Airgel 0.5%

Synthetic Amorphous Fine Silica 1.0%

Example B

wettable powder

Example C

Granules

Compound 1 10.0%

Attapulgite granules (low volatile matter, 0.71/0.30mm; 90.0%

U.S.S.No. 25–50 mesh)

Example D

extruded pellets

Example E

emulsifiable concentrate

Compound 1 10.0%

Polyoxyethylene sorbitan hexaoleate 20.0%

C ₆ -C ₁₀ fatty acid methyl ester 70.0%

Example F

microemulsion

Example G

suspension concentrate

Example H

water emulsion

Example I

oil dispersion

This disclosure also includes Examples A to I above, except that "Compound 1" is replaced by "Compound 2", "Compound 3", "Compound 4", "Compound 5", "Compound 6", "Compound 7" , "Compound 8", "Compound 9", "Compound 10", "Compound 11", "Compound 12", "Compound 13", "Compound 14", "Compound 15", "Compound 16", "Compound 17" , "Compound 18", "Compound 19", "Compound 20", "Compound 21", "Compound 22", "Compound 23", "Compound 24", "Compound 25", "Compound 26", "Compound 27" , "Compound 28", "Compound 29", "Compound 30", "Compound 31", "Compound 32", "Compound 33", "Compound 34", "Compound 35", "Compound 36", "Compound 37" , "Compound 38", "Compound 39", "Compound 40" or "Compound 41". The test results show that the compounds of the present invention are highly active pre- and/or post-emergence herbicides and/or plant growth regulators. The compounds of the invention generally exhibit the highest activity for post-emergence weed control (ie applied after weed stalks have emerged from the soil) and pre-emergent weed control (ie applied before weed stalks emerge from the soil). In areas where complete control of all vegetation is desired, such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, airports, river banks, irrigation and other waterways, signboards, and around highway and rail structures, many of them are important Spectrum pre-emergence and/or post-emergence weed control has utility. Many of the compounds of the present invention are useful for the selective control of grasses and broadleaf weeds in crop/weed mixes via selective metabolism in crops and weeds, or targeting of physiological inhibitory sites in crops and weeds Spots are selectively active, or are selectively applied on or in mixed crop and weed environments. Those skilled in the art will recognize that preferred combinations of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. The compounds of the present invention may exhibit tolerance to important agricultural crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, maize (corn), sorghum, soybean, rice, oat, Peanuts, vegetables, tomatoes, potatoes, perennial crops including coffee beans, cocoa beans, oil palms, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapples, hops, tea and forests such as eucalyptus and Conifers (eg, loblolly pine), and turf species (eg, Kentucky bluegrass, St. Augustine grass, Kentucky fescue, and Bermuda grass). Compounds of the invention are useful in genetically transformed or selected crop plants to incorporate herbicide resistance, express proteins that are toxic to invertebrate pests (such as B. thuringiensis toxins), and/or express other usable traits. Those skilled in the art will appreciate that not all compounds have the same effect on all weeds. Alternatively, the subject compounds can be used to alter plant growth.

Since the compounds of the present invention have pre- and post-emergence herbicidal activity, in order to control undesired plants by killing or injuring them or slowing their growth, the compounds are generally applied by various methods involving the use of A herbicidally effective amount of a compound of the present invention or a composition comprising said compound and at least one surfactant, solid diluent or liquid diluent contacts the leaves or other parts of said undesired plants, or contacts said undesired plants. The environment, such as the soil or water in which the undesired plant is growing, or the soil or water surrounding the seeds or other propagules of the undesired plant.

The herbicidally effective amount of a compound of the present invention is determined by a number of factors. These factors include: the formulation selected, the method of application, the amount and type of vegetation present, growing conditions, and the like. Generally, the herbicidally effective amount of the compound of the present invention is about 0.001 kg/ha to 20 kg/ha, wherein the range of about 0.004 kg/ha to 1 kg/ha is preferred. Those skilled in the art can readily determine the herbicidally effective amount required for the desired degree of weed control.

In one common embodiment, the compounds of the present invention are applied to a locus comprising both desired vegetation (e.g., crops) and undesired vegetation (i.e., weeds), typically in formulated compositions. Each can be a seed, a seedling, and/or a larger plant (eg, soil) that is in contact with the growing medium. In this locus, compositions comprising a compound of the invention may be applied directly to the plant or parts thereof and/or to the growing medium in contact with the plant, especially for undesired vegetation.

Plant species and varieties of the desired vegetation in the locus treated with the compounds of the invention can be obtained by conventional propagation and propagation methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the genome of the plant. A transgene defined by its specific position in the plant genome is called a transformation event or transgenic event.

Plant cultivars genetically modified in loci that can be treated according to the invention include those that are resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or contain other desirable properties. Plants can be genetically modified to exhibit traits such as herbicide tolerance, insect tolerance, modified oil characteristics, or drought tolerance. Useful genetically modified plants comprising a single gene transformation event or a combination of transformation events are listed in Example C. Additional information for the genetic modifications listed in Example C can be obtained from publicly available maintained databases such as the U.S. Department of Agriculture.

The following abbreviations T1 to T37 are used for the traits of Example C. "tol." means "tolerance", "res." means "resistance", "mod" means "modified" and "herb." means "herbicide". "-" indicates that the entry is not available.

Example C

*Argentine canola (Brassica napus), **Polish cabbage (B.rapa), #Eggplant

Although most commonly the compounds of the invention are used to control undesired vegetation, contact of the desired vegetation with the compounds of the invention in the treated locus can result in a superadditive or synergistic effect with the genetic trait in the desired vegetation, Includes traits introduced through genetic modification. For example, resistance to phytophagous pests or plant diseases, tolerance to biotic/abiotic stress, or storage stability may be greater than expected for a genetic trait in a desired vegetation.

Compounds of the present invention may be mixed with one or more other biologically active compounds or agents, including herbicides, herbicides, agent safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molt inhibitors and rooting stimulators, chemical sterilants, semiochemicals, repellants, attractants Insecticides, pheromones, feeding stimulants, phytonutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi. Mixtures of the compounds of the invention with other herbicides can extend the range of activity against other weed species and inhibit the proliferation of any resistant organism types. The present invention therefore also relates to a composition comprising a compound of formula 1 (herbicidally effective amount) and at least one additional biologically active compound or agent (biologically effective amount), and said composition may also comprise a surfactant, a solid diluent at least one of a diluent or a liquid diluent. Other biologically active compounds or agents may be formulated into compositions comprising at least one of surfactants, solid diluents or liquid diluents. For the mixtures of the invention, one or more other biologically active compounds or agents can be formulated together with the compound of formula 1 to form a premix, or one or more other biologically active compounds or agents can be combined with the compound of formula The compounds of 1 are formulated separately and the formulations are combined (for example in a spray tank) prior to administration, or alternatively, are administered sequentially.

Mixtures of one or more of the following herbicides with the compounds of the invention may be especially useful for weed control: acetochlor, acifluorfen and its sodium salt, aclofen, acrolein (2-propenal) , alachlor, mofon, ametryn, amiflumezone, rimsulfuron, cypromic acid and its esters (eg, methyl, ethyl) and salts (eg, sodium, potassium), chloride Fampridine, Herbicide, Ammonium Sulfamate, Sabiphos, Astragalus, Atrazine, Trisulfuron-methyl, Flubutyramide, Grass, Grass-Ethyl, Bencarbazone, Fluoxetine Amine, furazone, bensulfuron-methyl-methyl, desanphos, bentazone, bicyclic sulcotrione, metazadone, flumetrione, azafen, bialaphos, bisfluben and its Sodium salt, webacil, bromobutyramide, bromoxynil, bromoxynil, bromoxynil caprylate, butachlor, fluprofen-methyl, afenfos, dimethon, butoxycyclone, Butachlor, carfentrazone, long-killed grass, triaflufen-ethyl, catechin, methoxypyramid, mebafen, chlorbromuron, plastic alcohol-methyl, chlorpyramid, chlorimuron-methyl- Ethyl, Chlortoluron, Chlorpropen, Chlorsulfuron, Dipropen-Dimethyl, Sukla, Indoxafen, Cycloheptapyr, Etsulfuron, Chlorofosinate, Cyclofenac Ketone, clethodim, clodinafop-propargyl, clomazone, chloroformamide, clopyralid, clopyralid-ethanolamine, chlorester sulfame-methyl, benzuron, cyanazine, cyclo Cyclopyrimorate, cyclopyrimorate, cyprosulfuron, cycloxydim, cyhalofop-methyl, 2,4-D and its butoxyethyl ester, butyl, isoctyl and isopropyl ester and its dimethylammonium, diethanolamine and triethanolamine salts, dimethuron, palapaquat, palapaquat-sodium, damaron, 2,4-DB and its dimethyl ammonium, potassium and sodium salts, betaine, diquat, dicamba and its diammonium Ammonium alkoxide, Dimethylammonium, Potassium and Sodium Salts, Dichonil, 2,4-Dipropionate, Dichlorophenoxypropionate-Methyl, Diclosulam, Dibendazole Methosulfate, Diflufenamide, diflufenazole hydrazone, oxazolone, dimethoxam, metolachlor, amethazone, xylenoxam, xylenoxam-P, thimethine, dimethyl Hypoarsinic acid and its sodium salt, dichloramine, terol, fenadil, dibromodiquat, dithiopyr, diuron, DNOC, indoacid, EPTC, valtracarb, butafluoxil Grass, ethametsulfuron-methyl, ethazimidone, beetfur, fluoroemulsion, ethimethuron-methyl, ethoxyfen, oxaprop-ethyl, oxaprop-P -Ethyl, fenoxasulfone, fenquinotrione, tetrazolamide, feuron, feuron-TCA, wheatgrass fluorine-methyl, wheatgrass fluorine-M-isopropyl, wheatgrass fluorine-M-methyl, pyrimsulfuron Fluorosulfon-methyl, fluroxyprop-butyl, fluroxyprop-P-butyl, pyrazafen-methyl, flucarbazone-methyl, flubisulfuron-methyl, fluoxaprop-butyl, fluthiazol Fluoxachlor, flupyridoxazone-ethyl, flupyridoxazone-ethyl, flumesulam, oxalic acid-amyl, propargyl fluflumeil, fluoride, fluoxyfen-ethylcarboxylate, flumifenpyr oxazol, fluridine sulfuron-methyl and its sodium salt, azadin, azadin-butyl, chlorpyrazone, fluroxazone, maketaron, furazone, Flumetachlor, Fomesafen, Foramsulfuron-methyl, Phyphos-Ammonium, Glufosinate-Ammonium, Glufosinate-Ammonium, Glufosinate-Ammonium, Glyphosate and its salts such as Ammonium, Isopropyl Ammonium, Potassium, Sodium (including sesquisodium) and trimethylsulfonium (alternatively named glufosinate), haclopyridine, haclopyridin-methyl, clopyrazosulfuron-methyl, fluorine Piethyloxyfop, fluopyroxyfop, hexazinone, imazamox-methyl, imazethapyr, imazethapyr, imazapyr, imidazaquin, imidazaquin-ammonium, imazethapyr, Imazethapyr-ammonium, pyrazosulfuron-methyl, indoxenil, triazine-indenachlor, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil caprylate, ioxynil-sodium, triazimenil, Isoproturon, isoxazone, isoxamid, isoxaflutole, isoxaflumele, lactofen, cyclopyridine, rituron, maleic hydrazide, MCPA and its salts ( For example, MCPA-dimethylammonium, MCPA-potassium, and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl, 2-methyl-4-chlorobutoxyethyl ester) and thioesters (e.g., ethylthiochloride esters), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), propionic acid, propionic acid-P, mefenamide, mesosulfame, mesosulfuron -Methyl, mesotrione, metabam-sodium, mefenacet, fenmetrione, metazachlor, bis-ether chloropyridone, methylbenthiuron, methylarsinic acid and its Calcium ions, monoammonium, monosodium and disodium salts, methyl sulfauron, pyranuron, xiugulong, metolachlor, metolachlor, sulfatrazone, methoxuron, Cyclo Jin, Metsulfuron-Methyl, Caodamet, Luguron, Napropanamine, Napropamide, Napropamide-M, Yicaosheng, Caobulong, Nicosulfuron, Dabafen, Pingcaodan, Flumisulfuron-methyl, Huangcaoxiao, Propyloxadiazone, Oxadiazole, Epoxysulfuron-methyl, Oxazicone, Ethoxyfluorfen, Paraquat Dichloride, Ketraman, Nonanoic Acid, Di Mevalazine, penoxsulam, mechlorazamide, penoxadiazone, fenpyramid, methoxam, methoxam, beetin, picloram, picloram-potassium, fenpyrid Ammonium, pinoxaden, diphenafos, pretilachlor, flurisulfuron-methyl, amfluralin, chlorfenapyrone, prometon, promethen, propachlor, propanil, oxazone Ester, Promethazine, Anilin, Promethachlor, Probensulfuron-methyl, Promethazone-methyl, Laxate, Profensulfuron, Flusulfuron-methyl, Dipyrafen, Metazachlor, Pyrazolesulfonyl , bifenpyr, pyrazolate, benzamconazole, pyrazosulfuron-ethyl, pyrimidine saflufenacil, barnyard grass, pyridate, cyclomethicone, nob methyl ether, pyriproxyfen, pyrimthio Pyrimisulfone-sodium, Roxasulfone, pyrisulfame, fast barnyardgrass, quinclorac, algaquinone, quizalofop-ethyl, quizalofop-P-ethyl , quizalofop-P-quizalofosyl ester, rimsulfuron-methyl, saflufenacil, sethoxydim, cyclomeuron, simazine, sizazone, sulcotrione, sulfentrazone, methylazine Sulfuron-methyl, Sulfuron-methyl, 2,3,6-TBA, TCA, TCA-Sodium, Phytoxamine, Tethhiuron, Tefurtrione, Tetrasulfone, Pyroxydim, Teclodim, Terbutin Tong, terbufen, deoxazone, metmethacet , thiazole nicotinic acid, thiatonsulfuron-methyl, thifensulfuron-methyl, fensulfuron, tiafenacil, fensulfuron, fenpyrazone, oxatrione, wild wheat cam, flucarbazone-methyl, trifensulfuron-methyl , triazin flufen-methyl, triclopyr-methyl, triclopyr, triclopyr-butoxyethyl, triclopyr-triethylammonium, imazacycline, grass dazin, trifluxyroxysulfuron , Trifluralin, Flusulfuron-methyl-methyl, Triflumesulfuron-methyl, Methazone, 3-(2-Chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl- 1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4- Methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3 -Pyridinecarboxamide, 7-(3,5-dichloro-4-pyridyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]p-diazepine Heterophen-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone ), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)iso Oxazole (formerly methioxolin), 3-[7-fluoro-3,4-dihydro-3-oxo-4-(2-prop-1-yl)-2H-1,4-benzoxazine -6-yl]dihydro-1,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione, 4-(4-fluorophenyl )-6-[(2-Hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H) -diketone, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2 -Methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N- (4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include biological herbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc.), Drechsiera monoceras (MTB -951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Pucciniathlaspeos Schub.

The compounds of the present invention can also be used in combination with plant growth regulators such as Avivitamin, N-(phenylmethyl) -1H-purin-6-amine, propionyl brassinolide, gibberellic acid, gibberellin A ₄ and A ₇ , hypersensitive protein, meperidine, prohexadione calcium, jasmone, sodium nitrophenolate and Trinexapac-ethyl-methyl.

General references to agricultural protectants (i.e., herbicides, herbicide safeners, insecticides, fungicides, nematicides, acaricides, and biologicals) include The Pesticide Manual, 13th Edition, edited by C.D.S. Tomlin, British Crop Protection Council, Farnham, Surrey, U.K., 2003, and The BioPesticide Manual, 2nd Edition, edited by L.G. Copping, British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments wherein one or more of these different mixing combinations are used, the weight ratio of the different mixing combinations (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (eg, ratios between about 1:30 and about 30:1). Those skilled in the art can readily determine by simple experiments the biologically effective amount of the active ingredient required to obtain the desired range of biological activity. Clearly, the inclusion of these additional components extends the spectrum of weed control beyond that which the compounds of Formula 1 control by themselves.

In some cases, combinations of compounds of the present invention with other biologically active (especially herbicidal) compounds or agents (i.e. active ingredients) can achieve a greater than additive (i.e. synergistic) effect on weeds, and/or on crops or other Plants are expected to achieve a less than additive (ie safening) effect. It is always desirable to reduce the amount of active ingredients released in the environment while ensuring effective pest control. The ability to use larger amounts of active ingredient to provide more effective weed control without causing undue crop damage is also desirable. When the application rates of the herbicidally active ingredients to achieve an agronomically satisfactory degree of weed control have a synergistic effect on weeds, such combinations can be advantageously used to reduce the cost of crop production and reduce the environmental load. Such combinations can advantageously be used to increase crop protection by reducing weed competition when safening of the herbicidally active ingredients takes place on the crop.

Of note are combinations of the compounds of the invention with at least one other herbicidally active ingredient. Of particular note are such combinations in which the other herbicidally active ingredient has a different site of action than the compound of the invention. In some cases, resistance management will be especially advantageous in combination with at least one other herbicidally active ingredient having a similar control spectrum but a different site of action. Accordingly, the compositions according to the invention may also comprise (in a herbicidally effective amount) at least one additional herbicidally active ingredient having a similar control spectrum but a different site of action.

The compounds of the present invention can also be used in combination with herbicide safeners to increase safety to certain crops. Boscalid, Diuron, Dichloropropenylamine, 5-(2,2-dichloroacetyl)-3,3,8-trimethyl-1,5-diazabicyclo[4.3.0] Nonan-9-one, O-phenylthiophosphonic acid O, O-diethyl ester, diphenhydrazol, fenoxazole, cloxamethoxazole, cloxamethoxazole, fluoxazoxime, oxamethoxazole, bisphenyl Oxazole acid, diethyl pyrrole diacid, 4-chlorophenyl methyl carbamate, methoxybenzone naphthalene dicarboxylic anhydride (1,8-naphthalene dicarboxylic anhydride), oxanitrile, N-(aminocarbonyl )-2-methylbenzenesulfonamide, N(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloro-methyl)-sulfonyl]benzene (BCS), 4-(dichloro Acetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191) , 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylic acid ethyl ester, 2-hydroxy-N,N-dimethyl-6 -(trifluoromethyl)pyridine-3-carboxamide, and 1-(3,4-dimethylphenyl)-l,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylic acid 3-Oxo-1-cyclohexen-1-yl ester. An antidote effective amount of a herbicide safener may be applied simultaneously with the compound of the invention, or as a seed treatment. Accordingly, one aspect of the present invention pertains to herbicide mixtures comprising a compound of the present invention and an antidote effective amount of a herbicide safener. Seed treatments are particularly useful for selective weed control because it physically confines the detoxification effect to the crop plants. Accordingly, a particularly useful embodiment of the invention is a method for selectively controlling undesired vegetation growth in a crop comprising contacting the locus of said crop with a herbicidally effective amount of a compound of the invention, wherein said crop has grown from its The grown seeds are treated with a safener in a detoxifyingly effective amount. The antidote effective amount of a safener is readily determined by a person skilled in the art by simple experimentation.

Of note are compositions comprising (herbicidally effective amount) a compound of the invention, (effective amount) at least one additional active ingredient selected from other herbicides and herbicide safeners, and at least one selected from Components of surfactants, solid diluents and liquid diluents.

For better control of undesired vegetation (e.g. due to a synergistic effect such as reduced use rates, broader weed control, or enhanced crop safety) or to avoid the growth of herbicide-resistant weeds, the compounds according to the invention are preferably combined with Herbicide mixture.

Table Al lists specific combinations of component (a) and component (b) that exemplify the mixtures, compositions and methods of the invention. Compound 1 in the component (a) column is identified in Index Table B. The second column of Table Al lists specific component (b) compounds (eg "2,4-D" in the first row). The third, fourth and fifth columns of Table A1 list the weight ratio ranges relative to component (b) when the compound of component (a) is typically applied to field-grown crops (i.e. (a): (b)). Thus, for example, the first row of Table A1 specifically discloses that the combination of component (a) (i.e. compound 1 in Index Table B) and 2,4-D is typically in a weight ratio between 1:192–6:1 apply. The remaining rows of Table A1 are structured in a similar manner.

Table A1

Table A2 is constructed as Table A1 above, except that the entries under the column heading "Component (a)" are replaced by the corresponding component (a) column entries shown below. Compound # in column Component (a) is indicated in Index Tables A and B. Thus, for example, the entries below the column heading "Component (a)" in Table A2 are all listed as "Compound 6" (i.e., Compound 6 as indicated in Index Table B), and the first row below the column heading in Table A2 Specifically disclosed are mixtures of compound 6 and 2,4-D. Tables A3 to A41 are similarly constructed.

The following tests demonstrate the control efficacy of the compounds of the invention against specific weeds. However, the weed control provided by the compounds is not limited to these species. See Index Table A for compound descriptions. The following abbreviations are used in the index tables as follows: _CF3 is trifluoromethyl, Pyr is pyridyl, n is positive, Et is ethyl, Pr is propyl, _CF3 is trifluoromethyl, Pyr is pyridine group, and Ph is phenyl. The abbreviation "Ex." stands for "Example" and is followed by a number indicating the Example in which the compound was prepared.

index table A

a ES ⁺ , b ES ⁻ , c AP ⁺ .

*See Index Table C for ¹ H NMR data.

*See synthetic example for ¹ H NMR data.

index table B

a ES ⁺ , b ES ⁻ , c AP ⁺ .

*See Index Table C for ¹ H NMR data.

index table C

a ¹ H NMR data are in ppm downfield from tetramethylsilane. Couplings are indicated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet and (bs)-broad singlet.

Biological Examples of the Invention

Test A

Barnyardgrass (Echinochloa crus-galli), crabgrass, large (Digitarias anguinalis), Kochia scoparia (Kochia scoparia), ragweed (Hogweed, Ambrosia elatior), foxtail, gigantic (Great foxtail, Setaria faberii), morning glory (Ipomoea spp.), quinoa (Amaranthus retroflexus), downleaf (Abutilon theophrasti), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), wheat (Triticum aestivum), and corn (Zea mays) Seeds of the plant species were planted in a loamy soil and sand blend and treated pre-emergence with a directed soil spray using the test chemicals formulated in a non-phytotoxic solvent mixture containing surfactants.

Simultaneously, plants selected from these crop and weed species as well as Alopecurus myosuroides and catchweed bedstraw (Galium aparine) were planted in pots containing the same blend of loam and sand, and used for Test compounds formulated in the same manner were applied post-emergence to the treatment. Post-emergence treatments were performed using plants ranging in height from 2 cm to 10 cm and at the one- to two-leaf stage. Treated plants and untreated controls were kept in the greenhouse for about 10 days, after which all treated plants were compared with untreated controls and damage was assessed visually. The plant response scores summarized in Table A are based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (–) response indicates no test results.

test B

Plant species selected from Oryza sativa, small-flower umbrella sedge (Cyperus difformis), Heteranthera limosa and Echinochloa crus-galli were used in flooded paddy field tests. Grow to the 2-leaf stage for testing. At the time of treatment, the test pots were filled with water to 3 cm above the soil surface, treated by applying the test compound directly to the field water, and then maintained at this water depth for the duration of the test. Treated plants and controls were kept in the greenhouse for 13 to 15 days, after which all species were compared to controls and visually assessed. The plant response scores summarized in Table B are based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (–) response indicates no test results.

test C

Will be selected from black grass (Alopecurus myosuroides), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), wheat (winter wheat, Triticum aestivum), succulents (Alopecurus myosuroides, Galium aparine), maize (Maize (Zea mays)), weeds, large (Sorghum halepense, Digitaria sanguinalis), Foxtail, huge (Setaria faberii), Johnson grass (Sorghum halepense), Ashweed (Chenopodium album), Morning Glory (Ipomoea coccinea), Sedge, Yellow (Yellow Sedge, Cyperus esculentus), Chenopodium (Amaranthus retroflexus )), ragweed (hogweed, Ambrosia elatior), soybean (Glycine max), barnyardgrass (Echinochloa crus-galli), canola (Brassica napus), water hemp (common Seeds of the plant species of water cannabis, Amaranthus rudis (Amaranthus rudis), and velvet leaves (Abutilon theophrasti) were planted in a blend of loamy soil and sand and treated pre-emergence with a Treatment with test chemicals formulated in a non-phytotoxic solvent mixture.

At the same time, selected from these crops and weed species as well as chickweed (Common Chickweed, Scherichia (Stellariamedia)), oats, wild (Wild Oats, Portuguese Wild Oats (Avena fatua)), and Kochia (Broomweed) (Kochiascoparia)) plants are grown in the containing Sunshine The test chemicals formulated in the same manner were treated in pots with a pre-emergence application in a planting medium comprising sphagnum moss, vermiculite, starting nutrients and dolomitic limestone. Post-emergence treatments were performed using plants in the height range of 2 cm to 18 cm (one to four leaf stage). Treated plants and controls were kept in the greenhouse for 13 to 15 days, after which all species were compared to controls and assessed visually. The plant response scores summarized in Table C are based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (–) response indicates no test results.

The plant species in the flooded rice field test consisted of rice (Oryza sativa), small-flower umbrella sedge (Cyperus difformis), Heterantheralimosa and barnyardgrass grown to the 2-leaf stage for testing (Echinochloa crus-galli) composition. For treatment, the test pots were filled with water to 3 cm above the soil surface, treated with the test compound applied directly to the field water, and then maintained at this water depth for the duration of the test.

Treated plants and controls were kept in the greenhouse for 13 to 15 days, after which all species were compared to controls and visually assessed. The plant response scores summarized in Table C are based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (–) response indicates no test results.

test D

Will be selected from bluegrass (annual bluegrass, Poa annua), black grass (Alopecurus myosuroides), golden grass (Phalaris minor), chickweed (common chickweed, chickweed) (Stellaria media)), Soleweed (Galium aparine, Galium aparine), Bromus, Down (Bromus tectorum, Bromus tectorum), Russian thistle (Bromus tectorum) (Salsola kali)), wild poppy (Papaver rhhoeas), wild violet (Viola arvensis), foxtail, greens (Setaria viridis), dead nettle (Papaver Hemp, Lamium amplexicaule), Ryegrass, Italian (Italian ryegrass, Lolium multiflorum), Kochia scoparia (Kochiascoparia), Ashweed (Chenopodium album), Canola (Brassica napus), Quinoa (Amaranthus retroflexus), Chamomile (Odorless Chamomile, Matricaria inodora), Possum (Bird's-eye Pona, Veronica persica) , barley, spring (spring barley, Hordeum vulgare), wheat, spring (spring wheat, common wheat (Triticum aestivum)), buckwheat, wild (wild buckwheat, Polygonum convolvulus), wild mustard (Xinjiang Wild Canola (Sinapisarvensis), Oats, Wild (Wild Oats, Portuguese Wild Oats (Avena fatua)), Radish, Wild (Wild Radish, Wild Radish (Raphanus raphanistrum)), Apera spica-venti, Barley , winter (winter barley, Hordeum vulgare), and wheat, winter (winter wheat, Triticum aestivum) plant species seeds planted in silt loam and pre-emergence with non-phytotoxic solvent mixtures containing surfactants Test chemical treatments.

At the same time, plant these species in the The pots were planted in a planting medium comprising sphagnum moss, vermiculite, starter nutrients and dolomitic limestone, and treated with a test compound formulated in the same manner for post-emergence application. Plant heights ranged from 2 cm to 18 cm (1-leaf to 4-leaf stages). Treated plants and controls were maintained in a controlled growth environment for 14 to 21 days, after which all species were compared to controls and visually assessed. The plant response scores summarized in Table D are based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (–) response indicates no test results.

Test E

Will be selected from corn (Zea mays), soybean (Glycine max), gray vegetable (Chenopodium album), poinsettia, wild (wild poinsettia, Euphorbia heterophylla), quinoa, palmer (Palmer quinoa, Amaranthus palmeri), water hemp ( Common water marijuana, Amaranthus rudis), Suriname grass (Brachiaria decumbens), weed, large (Brachiaria sanguinalis), weed, Brazil (Brazilian weed, Digitaria horizontalis), millet, autumn (Fall millet, Panicum dichotomiflorum) Foxtail grass, giant (Setaria faberii), foxtail grass, green foxtail grass (Setaria viridis), cricket grass (Eleusine indica), Jiangsen grass (Sorghum halepense), ragweed (Hogweed, Ambrosia elatior) , Barnyardgrass (Echinochloa crus-galli), Tribulus (Cenchrus echinatus), Arrowleaf, Sida rhombifolia, Ryegrass, Italian (Lolium multiflorum), Commelina, Vegeta Coccinea (Commmelina virginica), Wild bindweed (Convolvulus arvensis), Cocklebur (Common cocklebur, Xanthium strumarium), Morning glory (Ipomoea coccinea), Nightshade (Eastern nightshade, Solanum ptycanthum), Kochia scoparia (Kochia scoparia), sedge, yellow (Yellow sedge, Cyperus esculentus), nettle (ladysthumb nettle, Polygonum persicaria), downy leaf (Abutilon theophrasti), little wineweed (Conyzacanadensis), and ghost Seeds of the plant species of needle grass (Bidens pilosa) were planted in silt loam and treated prior to emergence with test chemicals formulated in a non-phytotoxic solvent mixture containing surfactants.

Simultaneously, plants from these crops and weed species as well as Aquacannabis_RES1 (Common Aquacannabinoids Resistant to ALS & Triazines, Amaranthus rudis), and Aquacannabinoids_RES2 (Common Aquacannabinoids Resistant to ALS & HPPD, Amaranthus rudis) were grown in a field containing Sunshine The test chemicals formulated in the same manner were treated in the pots with a pre-emergence application in a growing medium containing sphagnum moss, vermiculite, starting nutrients and dolomitic limestone. Plant heights ranging from 2 cm to 18 cm (1-leaf to 4-leaf stages) were used for post-emergence treatments. Treated plants and controls were kept in the greenhouse for 14 to 21 days, after which all species were compared to controls and assessed visually. The plant response scores summarized in Table E are based on a 0 to 100 scale, where 0 is no effect and 100 is complete control. A dash (–) response indicates no test results.

Claims (15)

1. A compound selected from formula 1, its N-oxide and salt thereof, in X is R ¹ , and Y is -Q ¹ -J ¹ ; or X is -Q ² -J ² , and Y is R ² ; R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₄ hydroxyalkyl or C ₃ -C ₆ ring alkyl; Q ¹ is C(R ⁴ )(R ⁵ ), O, S or NR ⁶ ; R ² is halogen, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₄ alkoxyalkyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ Haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, C ₂ -C ₆ alkylcarbonyloxy, C ₁ -C ₄ hydroxyalkyl, S(O) _n R ³ , C ₂ -C ₄ alkylthioalkyl, C ₂ -C ₄ alkylsulfonylalkyl, C ₁ -C ₄ alkylamino, C ₂ -C ₄ dialkylamino or C ₃ -C ₆ cycloalkyl; Q ² is C(R ^4′ )(R ^5′ ); Each of J and J is independently a ⁶ -membered aromatic heterocyclic ring substituted with ¹ R ⁷ and optionally substituted with up to 2 R ⁸ on a carbon ring member; or substituted by 1 R on a carbon ring member A 5-membered aromatic heterocyclic ring substituted by R ⁹ and R ¹¹ on the nitrogen ring member and optionally substituted by 1 R ¹⁰ on the carbon ring member; A is phenyl substituted by up to 4 R ¹⁶ ; or a 5- or 6-membered aromatic heterocyclic ring substituted by up to 3 R ¹⁶ on the carbon ring member and R ¹⁷ on the nitrogen ring member; R ³ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; Each R ⁴ and R ^4' is independently H, F, Cl, Br, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or CO ₂ R ¹³ ; Each R ⁵ and R ^5' is independently H, F, C ₁ -C ₄ alkyl, OH or OR ¹³ ; or R ⁴ and R ⁵ or R ^4' and R ^5' are taken together with the carbon to which they are attached to form C(=O), C(=NOR ¹³ ) or C(=NN(R ¹⁴ )(R ¹⁵ )) ; R ⁶ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or S(O) _p R ¹⁸ ; Each R ⁸ is independently halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, or S(O) _p R ¹⁹ ; or ^R7 and ^R8 are taken together to form a 5 membered carbocyclic ring comprising ring members selected from up to two O atoms or up to two S atoms, and optionally replaced on carbon atom ring members by up to Five halogen atoms are substituted; R ⁹ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ haloalkoxy, or S(O) _p R ¹⁸ at the meta position where the ring is attached to the rest of Formula 1; R ¹⁰ is halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or S(O) _p R ¹⁹ ; R ¹¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; each R ¹³ is independently C ₁ -C ₄ alkyl; R ¹⁴ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; R ¹⁵ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; Each R ¹⁶ is independently H, halogen, cyano, nitro, SF ₅ , C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy or S(O) _p R ²⁰ ; Each R ¹⁷ is independently H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; each R ¹⁸ is independently C ₁ -C ₄ haloalkyl; Each R ¹⁹ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; R ²⁰ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; n is 0 or 1; and each p is independently 0, 1 or 2; The proviso is that when R1 is ethyl and Q1 is _CH2 , then J1 is not ³ -trifluoromethyl- ^1H -pyrazol- ¹ -yl. 2. The compound according to claim 1, wherein Each J ¹ or J ² is independently selected from 3. The compound according to claim 2, wherein X is R ¹ , and Y is -Q ¹ -J ¹ ; R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ alkenyl or C ₂ -C ₄ alkynyl; Q ¹ is C(R ⁴ )(R ⁵ ) or O; R4 is H ^; R ⁵ is H or OH; R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; A is phenyl substituted with up to 2 R ¹⁶ ; and Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen. 4. The compound according to claim 3, wherein R ¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; Q ¹ is C(R ⁴ )(R ⁵ ); R ⁵ is H; J1 is J- ² ; R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; ^A is phenyl substituted by 1 R; and R ¹⁶ is CF ₃ or F. 5. The compound according to claim 3, wherein R ¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; Q ¹ is O; R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; A is phenyl substituted with up to 2 R ¹⁶ ; and Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen. 6. The compound according to claim 5, wherein R ¹ is phenyl, ethyl or methyl; J1 is J- ² ; ^R7 is _CF3 ; ^A is phenyl substituted by 1 R; and R ¹⁶ is CF ₃ or F. 7. The compound according to claim 2, wherein X is -Q ² -J ² , and Y is R ² ; R ² is C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl; Q ² is C(R ^4′ )(R ^5′ ); R ^4' is H; R ^5' is H; R ⁷ is SF ₅ , C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; A is phenyl substituted with up to 2 R ¹⁶ ; and Each R ¹⁶ is independently C ₁ -C ₄ haloalkyl or halogen. 8. The compound according to claim 7, wherein R ² is C ₁ -C ₄ alkoxy; J2 is selected from J- ² , J-12, J-17, J-18, J-20 and J-22; R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; ^A is phenyl substituted by 1 R; and R ¹⁶ is CF ₃ or F. 9. The compound according to claim 7, wherein R ² is C ₁ -C ₄ alkoxy; J ² is J-2; R ⁷ is C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; ^A is phenyl substituted by 1 R; and R ¹⁶ is CF ₃ or F. 10. The compound according to any one of claims 6, 7, 8 and 9, wherein R ¹⁶ is at the para position where the benzene ring is attached to the rest of Formula 1. 11. The compound of claim 1, selected from the group consisting of: 4-[[5-Ethyl-3-[4-(trifluoromethyl)phenyl]-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl ) pyridine; 4-[[3-(4-fluorophenyl)-5-propyl-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine; 4-[[5-ethoxy-3-(4-fluorophenyl)-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine; 4-[[3-(4-fluorophenyl)-1-propyl-1H-1,2,4-triazol-5-yl]methyl]-2-(trifluoromethyl)pyridine; and 4-[[3-(4-fluorophenyl)-5-methoxy-1H-1,2,4-triazol-1-yl]methyl]-2-(trifluoromethyl)pyridine. 12. A herbicidal composition comprising a compound according to claim 1 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents agent. 13. A herbicidal composition comprising a compound according to claim 1, at least one additional active ingredient selected from other herbicides and herbicide safeners, and at least one selected from surface Components of Active Agent, Solid Diluent and Liquid Diluent. 14. A herbicidal mixture comprising (a) a compound according to claim 1, and (b) at least one additional active ingredient selected from (b1) to (b16 ) and salts of compounds of (b1) to (b16). 15. A method for controlling undesired vegetation growth, said method comprising contacting said vegetation or its environment with a herbicidally effective amount of a compound according to claim 1 .